CN109320090B - Method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag - Google Patents
Method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag Download PDFInfo
- Publication number
- CN109320090B CN109320090B CN201811317399.0A CN201811317399A CN109320090B CN 109320090 B CN109320090 B CN 109320090B CN 201811317399 A CN201811317399 A CN 201811317399A CN 109320090 B CN109320090 B CN 109320090B
- Authority
- CN
- China
- Prior art keywords
- chlorine
- blank
- slag
- hot slag
- containing titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C03C10/0009—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 silica as main constituent
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- 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
Abstract
The invention provides a method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag. The method may comprise the steps of: cooling the chlorine-containing titanium extraction hot slag to obtain cold slag, crushing the cold slag to obtain blank making powder, or pretreating the cold slag and ingredients to obtain mixed powder, and then granulating, drying and grading the blank making powder or the mixed powder in granularity to obtain blank making granules, wherein the mass fraction of the cold slag in the mixed powder is more than 85%; pressing and molding the blank-making granules 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 chlorine-containing titanium extraction hot slag can be directly utilized, and the utilization rate of the hot slag is high; the production process has no three-waste discharge.
Description
Technical Field
The invention relates to the field of resource utilization of solid wastes, in particular to a method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag produced on site.
Background
The chlorine-containing titanium extraction hot slag is hot titanium extraction slag obtained by directly carbonizing titanium-containing blast furnace slag at high temperature and chlorinating at low temperature, the chlorine content of the hot titanium extraction slag is high, and the chlorine-containing titanium extraction slag (namely chlorine-containing titanium extraction cold slag) is classified as dangerous slag, wherein the chlorine-containing titanium extraction hot slag has great harm to soil, environment and the like.
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, 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 dechlorinating agent is added for roasting, and the added value of the dechlorinated products is low; and the chlorine-containing titanium extraction hot slag needs to be cooled and transported to a slag yard for accumulation, so that the cost is high, and the chlorine-containing titanium extraction cold slag occupies a large area in the slag yard and can cause great influence on the environment.
Therefore, the comprehensive utilization of the chlorine-containing titanium extraction hot slag is very important.
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 hot slag, wherein chlorides can be simultaneously recovered 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 hot slag. The method may comprise the steps of:
cooling and crushing the chlorine-containing titanium extraction hot slag to obtain blank making powder; granulating, drying and grading the blank-making powder to obtain blank-making granules; pressing and molding the blank-making granules 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 microcrystalline glass by using the chlorine-containing titanium extraction hot slag. The method may comprise the steps of: cooling the chlorine-containing titanium extraction hot slag to obtain cold slag, and pretreating the cold slag and ingredients to obtain mixed powder, wherein the mass fraction of the ingredients in the mixed powder is below 15%, namely the mass fraction of the cold slag is above 85%, and the ingredients can comprise a fluxing agent and/or a microcrystalline glass component replenisher; granulating, drying and grading the mixed powder to obtain blank-making granules; pressing and molding the blank-making granules 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 granulation may include mixing the mixed powder with water or a binder.
According to one or more exemplary embodiments of the present invention, the blank-making pellet may have a particle size of 40 to 250 μm and a water content of 3 to 6% (mass fraction).
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: the scrap material from the trimming and/or polishing is used as one of the raw materials. I.e. returned to the previous step for reuse, the mass fraction of waste in the powder may be less than 2%.
According to one or more exemplary embodiments of the present invention, the pre-treatment may include crushing, mixing. When the water content in the cold slag is high, the pretreatment can also comprise a drying link, wherein the drying temperature can be 80-120 ℃, and the drying time can be 7-13 hours.
The step of pulverizing may include crushing and pulverizing, and after pulverizing, classification of particle size may also be performed.
According to one or more exemplary embodiments of the present invention, the size classification may include sieving.
According to one or more exemplary embodiments of the present invention, the hot slag containing chlorine titanium extraction includes hot slag generated after a high temperature carbonization-low temperature chlorination process is performed on the titanium-containing blast furnace slag, and the step of cooling the hot slag containing chlorine titanium extraction includes: and (3) carrying out heat exchange in the conveying process of the chlorine-containing titanium extraction hot slag after the low-temperature chlorination procedure.
According to one or more exemplary embodiments of the invention, the method further comprises the steps of: the heat exchanged in the cooling step is used in the drying, i.e. in the drying of the granules obtained by granulation.
According to one or more exemplary embodiments of the present invention, the press-forming may include: uniformly spreading the blank-making granules in a mould at 250-720 kgf/cm2Maintaining 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 extraction hot slag may be 2-5%, and the mass fraction of the element Cl in the chlorine-containing titanium extraction hot slag may be TiO2The mass fraction of (A) may be 2-10%.
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 nucleating agent is not required to be added in the preparation process, and only a small amount of granulating agent is required to be added; the chlorine-containing titanium extraction hot slag can be well utilized, the accumulation of slag is avoided or reduced, and the utilization rate of the chlorine-containing titanium extraction hot 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 microcrystalline glass by using chlorine-containing titanium extraction hot 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-extracting hot slag according to another exemplary embodiment of the invention;
FIG. 3 shows an X-ray diffraction pattern of a microcrystalline glass sample prepared from a hot slag containing titanium chloride;
FIG. 4 shows another X-ray diffraction pattern of a microcrystalline glass sample prepared from a hot slag containing titanium chloride;
FIG. 5 shows a scanning electron microscope image of a microcrystalline glass sample prepared from the chlorine titanium-containing hot slag;
figure 6 shows another X-ray diffraction pattern of a microcrystalline glass sample prepared with hot slag containing titanium chloride.
Detailed Description
Hereinafter, the method for producing glass ceramics using hot slag containing titanium chloride according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
The chlorine-containing titanium extraction hot 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 main components of the chlorine-containing titanium extraction hot slag are 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 hot slag containing chlorine for extracting titanium-2-5% of (A), Cl-CaCl is mainly used in the chlorine-containing titanium extraction hot slag2The chlorine-containing titanium-extracting slag has certain normal-temperature moisture absorption after being cooled, so that the chlorine-containing titanium-extracting slag can play a certain role in granulation and bonding in the granulation process.
Therefore, the invention provides a method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot 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 hot slag. Fig. 1 shows a schematic flow chart of a method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag according to an exemplary embodiment of the invention.
In an exemplary embodiment of the invention, the method may comprise the steps of:
and (3) cooling the chlorine-containing titanium extraction hot slag to obtain cold slag, and pretreating the cold slag to obtain blank making powder, or pretreating the cold slag and the ingredients serving as treatment objects to obtain mixed powder, as shown in step S01 in fig. 1. The cold slag is at a temperature of 100 ℃ or less, or 100 to 200 ℃ relative to the hot slag. When the treatment object contains cold slag and ingredients, the pretreatment may include pulverization and mixing; the particle size of the powder obtained after the grinding is 40-100 μm, and further 45-96 μm. When the water content in the cold slag is higher, the cold slag needs to be dried. The mass fraction of the ingredients in the mixed powder can be below 15 percent, namely the mass fraction of the chlorine-containing titanium-extracting slag can be above 85 percent, so that the requirement of high utilization rate of solid wastes can be met. 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 choice, 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 components. 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 (3) granulating, drying and grading the blank making powder or the mixed powder to obtain blank making granules with the granularity of 40-250 mu m and the water content of 3-6%, as shown in step S02 in figure 1. The drying may be performed simultaneously with the granulation, or may be performed after the granulation. After granulation, the powder is changed into an aggregate consisting of fine particles, water or a binder and air, the granularity of the blank-making granules is controlled to be 40-250 mu m, and when the granularity is controlled to be within the range, the blank-making granules have good grain composition, can improve the fluidity and are beneficial to subsequent blank making; further, the grain size of the blank-making granules can be 60-150 μm.
And (4) pressing and forming the blank granules to obtain a microcrystalline glass blank, as shown in step S03 in figure 1. The step of press forming may comprise: uniformly spreading the blank-making granules 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 S04 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, to ensure nucleation and crystallization of the blank, then continuing to heat 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 problems of high energy consumption, low efficiency and the like caused by too low heating speed are solved. Controlling the temperature and the heat preservation time of the low-temperature stage at 800-1000 ℃ for 30-60 min, so as to be beneficial to the nucleation and crystallization of the blank; and (3) keeping the temperature and the time at the high-temperature stage at 1100-1200 ℃ for 30-90 min, so that the green body can be sintered compactly. The step of cooling may comprise slow cooling to room temperature (or ambient)Temperature), or slow cooling first and then 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.
In this embodiment, the pulverization in the pretreatment may include crushing, pulverizing; it may even include classification to obtain a powder of suitable particle size.
In the embodiment, the hot slag containing chlorine and titanium dioxide can comprise the following components in percentage 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 temperature of the hot slag containing chlorine and titanium extraction from the low-temperature chlorination process can be 300-500 ℃. The state and treatment of the cooled cold slag have the following three conditions:
(1) the temperature of the cooled slag is 100-200 ℃. The water absorbing moisture of the chlorine-containing titanium-extracting slag is adsorption water, and the desorption temperature of the adsorption water is between 100 and 200 ℃, so that the chlorine-containing titanium-extracting slag cannot absorb water from air, namely, the cold slag cannot absorb moisture, and therefore, the cold slag does not need to be dried in the subsequent pretreatment.
(2) The temperature of the cooled slag is below 100 ℃, and the time interval between cooling and pretreatment is short. The water content in the cold slag is also very low due to the short time interval, so that the cold slag does not need to be dried in the subsequent pretreatment.
(3) The temperature of the cooled slag is below 100 ℃, but the time interval between cooling and pretreatment is longer. The water content absorbed by the cold slag is high, and when the water content in the cold slag is higher than 6%, the crushing link in the pretreatment can be affected, and the cold slag needs to be dried in the pretreatment.
Preferably, the temperature and treatment of the cold slag can be selected from both (1) and (2). Because the cold slag contains no water or little water, the cold slag does not need to be dried, and compared with the conventional pretreatment of the microcrystalline glass raw material, the energy for drying can be greatly saved. Moreover, the invention can be directly connected with the low-temperature chlorination process, namely, the system can be directly arranged near the low-temperature chlorination equipment, and the original cost for transporting the chlorine-containing titanium-extracting slag can be saved. Meanwhile, the land occupied by the chlorine-containing titanium-extracting slag does not need to be increased, and further the damage of the slag to the land is reduced. Further preferably, the temperature and treatment of the cold slag may be selected (2) to reduce or avoid adverse effects of excessive temperatures on the equipment. The pulverization and the compounding in the pretreatment may be performed in no order.
In this embodiment, since the chlorine-containing titanium-extracting slag (i.e., the cooled chlorine-containing titanium-extracting hot slag or cooled slag) has moisture absorption, the moisture-absorbing water of the chlorine-containing titanium-extracting slag in the pretreatment process can play a role of a certain binder, and meanwhile, the binding effect generated by the water is beneficial to the generation of agglomeration of small particles and granulation and subsequent compaction, and the granulation process is actually to aggregate fine powder particles into granules through the binding effect. Due to the moisture absorption, the water content of the chlorine-containing titanium-extracting slag is increased by 1-2% before granulation, and the longer the time before granulation, the higher the water content. Therefore, in the raw material granulation process, the water introduced by the moisture absorption effect can reduce the addition amount of the binder or the water, which is beneficial to reducing the cost and improving the uniformity of the water in the granules.
In this embodiment, if the hot slag (i.e. the hot slag containing chlorine and titanium dioxide) is directly mixed with the batch, the two may generate a physicochemical reaction, and the composition of the batch changes, which will affect the subsequent firing of the glass ceramics. It is therefore necessary to cool the hot slag, exchanging part of the heat (or thermal energy) of the hot slag.
The cooling process may include:
(1) and cooling the chlorine-containing titanium extraction hot slag in the conveying process. Wherein the content of the first and second substances,
during the transportation process of the hot slag containing chlorine and titanium extraction before being transported to a pretreatment device (such as a crushing device), part of the heat of the hot slag containing chlorine and titanium extraction can be exchanged by a heat exchanger. The conveyer belt of the conveyer and the linings of the crusher and the crusher can be made of high-temperature-resistant and corrosion-resistant materials, and particularly can be used for a long time within the range of 100-200 ℃ and is resistant to acid corrosion.
(2) Directly blast and cool the chlorine-containing titanium extraction hot slag, and simultaneously can collect the hot air after blast.
In this embodiment, the heat exchanged by cooling can be used in at least one of the following steps.
(1) When the crushing of the cold slag is affected by the high water content in the cold slag, the exchanged heat (such as the heat exchanged by the heat exchanger or the hot air after air blast) can be used for drying the cold slag.
(2) Due to the fact that water or a binder is introduced in the granulating process, the water content of the granules is increased, and therefore the exchanged heat (such as heat energy exchanged by a heat exchanger or hot air after air blowing) can be used for drying after granulation, and the water content of the blank-making granules is guaranteed to be 3-6% so as to facilitate subsequent blank making.
(3) And (4) preheating the blank. The exchanged heat (e.g., heat exchanged by a heat exchanger or hot air after blowing) can be used to preheat the green body prior to heating the green body.
Therefore, the invention can fully utilize the heat energy of the chlorine-containing titanium extraction hot slag and reduce the energy consumption.
The method can be preferably used for adjacent drying links in view of reducing the laying of pipelines as much as possible in engineering and utilizing heat energy to the maximum extent. For example, it can be used preferentially in the closest possible cold slag drying stage, and secondly in the drying of the granulated granules, and again in the drying of the green body; when the cold slag does not need to be dried, the cold slag can be preferentially used for drying granules after granulation.
In this embodiment, if the raw material contains ingredients, the ingredients may be dry and contain no substances or components capable of absorbing water at normal temperature, so that the ingredients may not be dried during pretreatment. Besides the chlorine-containing titanium-extracting slag, the raw material or the blank making powder material can also comprise the following components in percentage 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 example, water or a binder may be added for granulation. The binder may include an aqueous solution of one of gum arabic, polyvinyl alcohol and carboxymethyl cellulose, and further, an aqueous solution of polyvinyl alcohol may be selected because of its low price in the early stage, wide applicability and easy adjustment of viscosity. In the polyvinyl alcohol solution, the mass ratio of polyvinyl alcohol to water is 5-10: 90-95, namely the concentration of the prepared polyvinyl alcohol solution is 5% -10%; granulating according to the proportion of adding 1-1.2L of polyvinyl alcohol solution into every 25-30 kg of pretreated blank making powder or mixed powder; namely, the proportion of the polyvinyl alcohol solution to the blank making powder or the mixed powder can be 1: 20-1: 30.
granulation is a process of producing aggregates with larger particle size by agglomeration of fine powder particles under the action of a binder or water. The granulation method can comprise a water adding granulation method, and specifically comprises the following steps: the dry mixed powder or blank making powder is conveyed to a granulator, a spray nozzle and a rotating shaft with blades are arranged in the granulator, when a mixer runs, a binder or water is sprayed to the powder in a fogdrop mode through the spray nozzle, and meanwhile, the rotating shaft with blades in the mixer can rotate rapidly, so that the contact frequency of the powder and the water or the binder is increased, and the powder and the water or the binder are mixed uniformly.
In this example, the water content of the pelletized and formed pellets should not be too high, or water in the pellets would flow out under pressure during the subsequent press forming, which would increase the corrosion of the mold. Therefore, the water content in the green pellets needs to be reduced to 6% or less, and further, to 5% or less by drying.
The water content in the blank-making granules is controlled to be 3-6%, further to be 4-5%. When the water content of the green pellets is less than 3%Under a pressure (e.g., 250 to 720 kgf/cm) in the green 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 example, the green powder or the mixed powder was granulated to become an aggregate of fine particles, water or a binder and air. Drying is required after granulation, which can homogenize the moisture distribution in the pellets and reduce the water content in the pellets. The drying time can be 1-3 h, and the temperature can be 80-120 ℃.
In this example, a size classification, for example a sieving, is carried out after drying. The particle size classification can obtain granules with particle sizes suitable for blank making; for example, the granules can be sieved by a sieve of 60 to 80 meshes, and the sieved part is taken as blank-making granules, and the granule size is 40 to 250 mu m.
For the granules with non-conforming particle size, further pulverization can be carried out to make the particle size meet the requirements. For example, the sieved fraction may be pulverized and sieved repeatedly until all passes.
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 can be returned as one of the raw materials. The cooling water generated by polishing and trimming can be recycled after precipitation.
In this embodiment, the heat treatment process may be performed in an oxygen-containing gas, such as air or an oxygen-rich gas.
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 the chlorine-containing titanium extraction hot slag can use the chlorine-containing titanium extraction hot slag or the chlorine-containing titanium extraction hot slag and ingredients as raw materials, obtain blank making powder through cooling and pretreatment, obtain blank making granules after granulating, drying and sieving the powder, perform dry pressing on the blank making granules to obtain a microcrystalline glass blank, perform low-temperature heating, high-temperature heating and cooling on the blank in a tunnel kiln, perform trimming, polishing and the like, and finally obtain a microcrystalline glass product.
Specifically, the method for preparing the glass ceramics can comprise the following steps:
1) and cooling the chlorine-containing titanium extraction hot slag to obtain cold slag, and then pretreating the cold slag and the 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 crushing, grinding, grading and the like. The cold slag and the ingredients can be respectively crushed, ground and graded and then matched, or can be matched firstly and then crushed. The cold slag and the ingredients form a batch which comprises the following components in percentage by mass: 85-100% of cold 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 granularity of the obtained powder for blank making is 45-96 mu m.
2) And (3) granulating, drying and sieving the powder for blank making (which can be cold slag powder or mixed powder) to obtain granules for blank making.
3) Uniformly spreading the granules 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 pellet for forming the blank 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.
4) 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 raw materials 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 direction of the airflow of the high-temperature heating section (1130-1185 ℃) of the tunnel kiln is opposite to that of the airflow of the low-temperature heating section, 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 reciprocating scraper conveyor can recover the chloride.
The microcrystalline glass prepared by the method of the two exemplary embodiments is subjected to an X-ray diffraction test, and the phases of the product can be found to comprise: 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. As shown in fig. 4, the akermanite phase is a main crystal phase, and the diopside phase and the perovskite phase are secondary 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.
FIG. 5 shows a scanning electron microscope image of a microcrystalline glass sample prepared from the chlorine titanium extraction hot slag, wherein the microcrystalline phase in the microcrystalline glass is mainly platy, 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, as shown in fig. 3, the microcrystalline phase of the crystallized glass may include a main crystalline phase: 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, as shown in fig. 6, 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: body densityThe degree of the reaction is 2.60 to 2.8g/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) and conveying the hot chlorine-containing titanium-extracting slag obtained from the low-temperature chlorination process to crushing equipment by a conveyor, and performing heat energy exchange on the chlorine-containing titanium-extracting slag by a heat exchanger in the conveying process. After conveying, reducing the temperature of the chlorine-containing titanium-extracting slag to 100 ℃, crushing, grinding and grading the chlorine-containing titanium-extracting slag and the ingredients, wherein the ingredients are quartz, potassium feldspar and borax, the ingredients are weighed and matched according to the mass percent of 85% of the chlorine-containing titanium-extracting slag, 5% of the quartz, 7% of the potassium feldspar and 3% of the borax, and powder with the granularity of 96 mu m is taken as mixed powder.
2) Conveying the mixed powder into a granulator, starting a spraying device above the granulator, spraying water on the mixed powder in a fogdrop mode, continuously stirring by a rotating shaft with blades, fully mixing and wetting the mixed powder and the water to form granules with a large amount of spherical granules and powder particles, discharging the granules, drying the granulated granules at 120 ℃ for 1h, sieving by an 80-mesh sieve, and repeatedly sieving the part on the sieve after crushing until the part on the sieve passes through the granules completely to obtain blank-making granules. Uniformly spreading the blank-making granules in a mould, and pressing under 714kgf/cm2And carrying out dry pressing molding under the pressing condition of the pressure maintaining time of 15s, 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 a heating rate of 5 ℃/min, preserving the heat for 60min, then slowly cooling with a kiln at 400 ℃, and cooling at a 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 test of the microcrystalline glass product shows that the density of the test body is 2.64g/cm3, the water absorption 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 method comprises the following steps of conveying chlorine-containing titanium extraction hot slag (the temperature is about 450 ℃) discharged by a low-temperature chlorination process to crushing equipment by a conveyor, carrying out heat energy exchange with the chlorine-containing titanium extraction hot slag by a heat exchanger in the conveying process, and using the exchanged heat energy for drying granulated granules, wherein the ingredients are selected from quartz, soda and polishing trimming waste. Then weighing and matching the chlorine-containing titanium-extracting slag and the dried ingredients according to the mass percentage of 90 percent of the chlorine-containing titanium-extracting slag, 3 percent of quartz, 5 percent of soda ash and 2 percent of polishing trimming waste, putting the matched materials into crushing equipment, and sequentially crushing, grinding and grading the materials in the crushing equipment, wherein powder with the granularity of 75 mu m is taken as mixed powder.
2) Conveying the mixed powder into a granulator, starting a spraying device above the granulator, spraying a binder on the mixed powder in a fogdrop mode, continuously stirring by a rotating shaft with blades, fully mixing and wetting the mixed powder, the binder and water to form granules with a large amount of spherical granules and powder particles, and drying the granules after granulation at 80 ℃ for 3 hours; sieving the dried granules with a 60-mesh sieve, pulverizing the sieved parts, sieving repeatedly until all the parts pass through,pellets for forming a green body were obtained. Uniformly spreading the blank-making granules in a mould, and pressing under 650kgf/cm2And carrying out dry pressing molding under the pressing condition of the pressure maintaining time of 30s, 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 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, preserving heat for 90min, and then slowly cooling to 450 ℃ along with a kiln, wherein the cooling rate is 1 ℃/min; and then rapidly cooling from 450 ℃ to 40 ℃, wherein the cooling rate is 8 ℃/min, 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 heating process from 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 obtained microcrystalline glass product is subjected to performance test, and the test shows that the microcrystalline glass product has the bulk density of 2.62g/cm3, the water absorption of 0.28 percent, the compressive strength of 105MPa, the acid resistance of 96 percent and the alkali resistance of 99.2 percent.
In conclusion, compared with the prior art, the method for preparing the microcrystalline glass by using the chlorine-containing titanium extraction hot slag has remarkable progress, and has the following beneficial effects:
1) according to the invention, the chlorine-containing titanium-extracting hot slag from the low-temperature chlorination process is directly utilized, so that the energy consumption for drying materials is saved, and the cost for cooling and transporting the chlorine-containing titanium-extracting slag is saved.
2) The technological process adopted by the invention comprises cooling → batching → granulating → blank making → low-temperature dechlorination → high-temperature sintering → polishing and trimming → product, 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 a melting sintering method and an integral crystallization method are avoided.
3) Relative to the melt-sintering process and the bulk precipitationCrystal method, TiO in hot slag raw material containing chlorine for extracting titanium used in the invention2With 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 hot slag is 85-100%.
4) The invention utilizes the characteristic of normal temperature moisture absorption of the chlorine-containing titanium slag, and can reduce the use of a binder.
5) 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.
6) The performance of the microcrystalline glass prepared by the method is higher than that of natural stone, and the microcrystalline glass can be used as high-grade building decorative materials, craft sculptures, functional ceramic materials and the like.
7) 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.
8) The method can directly utilize the heat energy of the chlorine-containing titanium extraction hot slag, and can reduce the accumulation of the chlorine-containing titanium extraction hot slag, thereby reducing the occupied land and reducing the harm to the 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 microcrystalline glass by using the chlorine-containing titanium extraction hot slag is characterized by comprising the following steps of:
cooling and crushing the chlorine-containing titanium extraction hot slag to obtain blank making powder;
granulating, drying and grading the blank-making powder to obtain blank-making granules;
pressing and molding the blank-making granules 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 hot 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 microcrystalline glass by using the chlorine-containing titanium extraction hot slag is characterized by comprising the following steps of:
cooling the chlorine-containing titanium extraction hot slag to obtain cold slag, and pretreating the cold slag and ingredients to obtain mixed powder, wherein the mass fraction of the ingredients in the mixed powder is below 15%, and the ingredients comprise a fluxing agent and/or a microcrystalline glass component replenisher;
granulating, drying and grading the mixed powder to obtain blank-making granules,
pressing and molding the blank-making granules 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 hot 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 hot slag as claimed in claim 2, wherein the pretreatment comprises crushing and mixing.
4. The method for preparing the glass-ceramic by using the chlorine-containing titanium extraction hot slag according to claim 1 or 2, wherein the grain size of the blank-making granules is 40-250 μm, and the water content is 3-6%.
5. The method for preparing the glass-ceramic by using the hot slag containing the chlorine titanium dioxide according to the claim 1 or 2, wherein the hot slag containing the chlorine titanium dioxide comprises hot slag generated after the titanium-containing blast furnace slag is subjected to a high-temperature carbonization-low-temperature chlorination process, and the step of cooling the hot slag containing the chlorine titanium dioxide comprises the following steps: and (3) carrying out heat exchange in the conveying process of the chlorine-containing titanium extraction hot slag after the low-temperature chlorination procedure.
6. The method for preparing the glass-ceramic by using the chlorine-containing titanium-extracting hot slag according to claim 5, characterized by further comprising the following steps: the heat exchanged from the cooling step is used in the drying.
7. The method for preparing the glass-ceramic by using the chlorine titanium-extraction-containing hot slag according to claim 1 or 2, wherein the step of press forming comprises the following steps:
uniformly spreading the blank-making granules in a mould at 250-720 kgf/cm2Keeping the pressure for 15-30 s, and then demoulding to obtain a blank.
8. The method for preparing the glass-ceramic by using the chlorine-containing titanium extraction hot slag as claimed in 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 ℃.
9. The method for preparing the microcrystalline glass by using the chlorine-containing titanium extraction hot slag as claimed in claim 1 or 2, wherein the step of heating to 1100-1200 ℃ comprises the following steps: heating to 1100-1200 ℃ at a heating rate of 3-5 ℃/min.
10. The method for preparing microcrystalline glass by using hot slag containing chlorine titanium dioxide according to claim 1 or 2, wherein Cl is contained in the hot slag containing chlorine titanium dioxideThe mass fraction of the elements is 2-5%, and TiO2The mass fraction of (A) is 2-10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811317399.0A CN109320090B (en) | 2018-11-07 | 2018-11-07 | Method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811317399.0A CN109320090B (en) | 2018-11-07 | 2018-11-07 | Method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109320090A CN109320090A (en) | 2019-02-12 |
| CN109320090B true CN109320090B (en) | 2022-02-11 |
Family
ID=65260939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811317399.0A Active CN109320090B (en) | 2018-11-07 | 2018-11-07 | Method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109320090B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112619887B (en) * | 2020-11-27 | 2023-03-31 | 西南科技大学 | Carbon extraction dechlorination method for titanium extraction slag and carbon extraction dechlorination tailings |
| CN114230184B (en) * | 2021-12-30 | 2023-07-14 | 武汉理工大学 | Microcrystalline glass with liquid titanium slag as main raw material and preparation method thereof |
| CN115636588A (en) * | 2022-10-26 | 2023-01-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing microcrystalline glass by extracting titanium tailings |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182120A (en) * | 2007-12-07 | 2008-05-21 | 内蒙古科技大学 | Method for manufacturing glass-ceramics |
| CN101323503A (en) * | 2008-07-22 | 2008-12-17 | 东北大学 | Method for preparing microcrystalline foamed glass by titanium-containing blast furnace slag |
| CN103145338A (en) * | 2013-03-27 | 2013-06-12 | 内蒙古科技大学 | Preparation method of blast furnace slag microcrystalline glass containing fluorine, potassium, sodium and rare earth |
| CN103922599A (en) * | 2014-03-06 | 2014-07-16 | 贵州大学 | Method for preparing microcrystalline glass by utilization of red mud-fly ash-titanium slag |
| CN106517798A (en) * | 2016-10-21 | 2017-03-22 | 北京科技大学 | Method for preparing glass-ceramic by use of medium-low titanium type blast furnace slag |
| CN108373266A (en) * | 2018-04-11 | 2018-08-07 | 四川名微晶科技股份有限公司 | A method of preparing devitrified glass new material using smelting titanium tailings |
| CN108423997A (en) * | 2018-06-13 | 2018-08-21 | 攀枝花学院 | The method for preparing crystallite foam glass using solid waste |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5046721A (en) * | 1973-08-08 | 1975-04-25 | ||
| CN101851063B (en) * | 2010-05-21 | 2012-05-02 | 郑州大学 | Technology for preparing microcrystal glass by utilizing blast furnace water granulated slag and coal ash |
| CN101891389B (en) * | 2010-07-22 | 2011-11-30 | 西南科技大学 | Chrysotile tailing microcrystal glass and preparation method thereof |
-
2018
- 2018-11-07 CN CN201811317399.0A patent/CN109320090B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182120A (en) * | 2007-12-07 | 2008-05-21 | 内蒙古科技大学 | Method for manufacturing glass-ceramics |
| CN101323503A (en) * | 2008-07-22 | 2008-12-17 | 东北大学 | Method for preparing microcrystalline foamed glass by titanium-containing blast furnace slag |
| CN103145338A (en) * | 2013-03-27 | 2013-06-12 | 内蒙古科技大学 | Preparation method of blast furnace slag microcrystalline glass containing fluorine, potassium, sodium and rare earth |
| CN103922599A (en) * | 2014-03-06 | 2014-07-16 | 贵州大学 | Method for preparing microcrystalline glass by utilization of red mud-fly ash-titanium slag |
| CN106517798A (en) * | 2016-10-21 | 2017-03-22 | 北京科技大学 | Method for preparing glass-ceramic by use of medium-low titanium type blast furnace slag |
| CN108373266A (en) * | 2018-04-11 | 2018-08-07 | 四川名微晶科技股份有限公司 | A method of preparing devitrified glass new material using smelting titanium tailings |
| CN108423997A (en) * | 2018-06-13 | 2018-08-21 | 攀枝花学院 | The method for preparing crystallite foam glass using solid waste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109320090A (en) | 2019-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109320090B (en) | Method for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag | |
| CN110396592B (en) | Method and device for baking lithium salt by using spontaneous combustion of lithium ore as heat source | |
| AU2019343956A1 (en) | Sintered geopolymer compositions and articles | |
| JPS6035292B2 (en) | glass manufacturing method | |
| CN1984734B (en) | Method for preparing particle flame-resistant composition | |
| CN105417950B (en) | A kind of fluxing nucleator of micro crystal material and preparation method thereof | |
| CN104556039A (en) | Method for preparing solid calcium carbide | |
| CN113402257A (en) | Formula and method for producing foamed ceramic by taking waste incineration fly ash as main body | |
| EA023830B1 (en) | Method for producing an agglomerate made of fine material containing metal oxide for use as a blast furnace feed material | |
| CN110511053A (en) | A kind of foamed ceramic and preparation method thereof using ceramics squeezing mud production | |
| EP0626349B1 (en) | Apparatus for making crystallized glass | |
| CN103214250B (en) | Recycling method for waste alumina brick | |
| CN109279782B (en) | System for preparing microcrystalline glass by using chlorine-containing titanium extraction hot slag | |
| CN108947258B (en) | Microcrystalline glass using chlorine-containing titanium extraction slag as raw material | |
| CN109133650B (en) | Method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag | |
| CN109133649B (en) | System for preparing microcrystalline glass by using chlorine-containing titanium extraction slag | |
| CN109133651B (en) | Microcrystalline glass prepared from chlorine-containing titanium extraction slag | |
| CN113292353A (en) | Method for preparing ceramsite by using nickel wet-process smelting slag | |
| CN109279783B (en) | Microcrystalline glass with raw materials including chlorine-containing titanium extraction slag | |
| CN106430982A (en) | Recycling method of glass ceramic material | |
| CN101941700B (en) | Method for removing boron impurity from industrial silicon | |
| CN113548842B (en) | Method for preparing baking-free brick by using ash | |
| CN108178519A (en) | A kind of novel foam glass and preparation method thereof | |
| CN114956799A (en) | Dry-method powder-making ceramic tile/board and preparation method thereof | |
| CN107793132A (en) | Ceramic Tiles based on ceramic polished slag and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |