CN112390526A - Method for harmlessly treating cyanided tailings in surface crystallization process of microcrystalline glass granules - Google Patents
Method for harmlessly treating cyanided tailings in surface crystallization process of microcrystalline glass granules Download PDFInfo
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- 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
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
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Abstract
The invention provides a method for harmlessly treating cyanided tailings by utilizing a crystallization process on the surface of microcrystalline glass granules, which comprises the following steps: performing two-stage roasting decyanation on the cyanide tailings after filter pressing, proportioning the decyanated cyanide tailings and auxiliary components, melting the batch mixture at high temperature to obtain glass liquid, uniformly clarifying the high-temperature glass liquid, granulating by using a granulator, and performing surface crystallization on the prepared glass particles in the air to form microcrystalline glass particles with a 'mantle' structure, wherein the surface of the microcrystalline glass particles is a crystal shell and the interior of the microcrystalline glass particles is an amorphous core, heavy metal elements in the cyanide tailings can be used as component phases in the crystal shell to form a new crystal phase, and the heavy metal elements in the amorphous core are solidified in a glass grid of the amorphous core. The microcrystalline glass particles can be used for preparing novel cementing materials and filling aggregate for mine cemented filling. The method can realize the heavy metal solidification of the cyanidation tailings and the comprehensive utilization of the microcrystalline glass solidified body.
Description
Technical Field
The invention relates to the technical field of hazardous waste disposal and comprehensive utilization, in particular to a method for harmlessly disposing cyanide tailings by utilizing a microcrystalline glass granule surface crystallization process.
Background
At the end of the 19 th century, MacArthur proposed a process for producing gold using dilute cyanide solutions to dissolve gold in gold ore and replace it with zinc metal, and established the world's first cyanidation gold extraction plant in africa. Since then, cyanidation gold extraction technology is generally applied to gold production in the world, and cyanidation gold extraction technology has become the main method for selecting and smelting modern gold mines. The cyanidation method is applied to gold extraction in early 20 th century in China, a 2 t/year cyanidation test plant is built at the Ministry of the Wehai Fangjia in Shandong in 1901, and after a new China is established, the cyanidation gold extraction technology is rapidly popularized in China and rapidly developed.
The most common cyanide used for dissolving gold ore is sodium cyanide, which is a highly toxic chemical, and the cyanidation tailings refer to tailings after gold extraction by cyanidation, which contains highly toxic sodium cyanide and other heavy metals and is characterized as dangerous solid waste. In the gold smelting industry of fluidized roasting, the total annual output of cyanidation tailings is about 170 plus 200 ten thousand tons, and the quantity is quite remarkable.
The cyaniding tailings contain As, Cd, Cu, Pb, Zn and CN-And valuable metal elements and toxic elements having high mobility, which are defined as hazardous wastes. Harmful components such as highly toxic substances, heavy metal elements and the like contained in cyanidation tailings are difficult to treat by conventional technology, and even if the harmful components can be treated, the cost is very high, so that the stockpiling is a treatment mode preferentially adopted by most gold enterprises at present. However, the stacking of the cyanidation tailings occupies a large amount of land, and seriously pollutes and harms the surrounding ecological environment such as soil, underground water and the like, the harm caused by the stacking of the cyanidation tailings is long-term, the stacking of the cyanidation tailings may not have adverse consequences temporarily, but the environment is more and more damaged along with the lapse of time, the later-stage treatment difficulty is higher than that in the earlier stage, and the life health and safety of people are greatly threatened.
The "national hazardous waste list" from 8.1.2016 lists "cyanidation tailings and cyanide-containing wastewater treatment sludge generated during gold beneficiation using cyanide" in the hazardous waste list (waste code: 092-003-33). The domestic process method for treating the dangerous solid wastes mainly comprises the following steps: solidification, safe landfill, surface treatment (natural degradation by mixing with soil), high-temperature incineration, pyrolysis (mainly used for organic matters), marine treatment (ocean dumping and ocean incineration), chemical treatment and the like. Aiming at dangerous solid waste such as cyaniding tailings, the gold industry cyanogen slag pollution control technical specification implemented from 3 and 1 of 2018 requires that the cyanogen content in cyaniding tailings stored in a warehouse is not higher than 5mg/L, and the warehouse management, the warehouse-down transportation and the like of the cyaniding tailings are specified. The gold industry cyanogen slag pollution control technical specification gives cyanidation tailing treatment technology, such as hydrogen peroxide oxidation method, biological method, inconel method, cyanogen reduction precipitation method, chlorine oxidation method and the like. The cyanogen reduction treatment technology recommended in the gold industry cyanogen slag pollution control technical specification can only reduce the content of cyanides to the warehousing and stockpiling standard, or has high treatment cost.
In recent years, many units have studied the harmless disposal and resource comprehensive utilization of the cyanide tailings, but basically, the cyanide tailings are subjected to cyanide breaking treatment or only the landfill of the cyanide tailings is realized, for example, a patent document with publication number CN 111589842A discloses a harmless disposal process of cyanide tailings incineration, and the cyanide tailings are used for cement production; further, patent document No. CN 109650595A discloses harmless treatment of cyanidation tailings by a "two-blow one-wash" treatment process, and the treatment process is used for underground filling.
At present, the main method for disposing cyanide tailings in the gold smelting industry is to temporarily stack or export the cyanide tailings in a dangerous solid waste tailings pond to a qualified cement plant for treating and producing cement, and the cyanide tailings contain highly toxic cyanide, so that the qualified cement plant has a very limited demand. How to realize the comprehensive utilization process of 'harmlessness', 'reduction' and 'recycling' of the cyanidation tailings, the treatment problem of the cyanidation tailings is thoroughly solved, and especially the heavy metal elements in the cyanidation tailings become a great challenge for gold production enterprises.
In order to solve the problems, the invention provides a method for harmlessly treating cyanide tailings by utilizing a microcrystalline glass granule surface crystallization process, cyanide in the cyanide tailings can be removed, microcrystallization and solidification of heavy metal are realized, harmful elements can reach the national standard (GB 5085-3-2007) hazardous waste identification standard after treatment, and the obtained microcrystallized glass granules can be used for producing novel cementing materials for mine filling.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for harmlessly treating cyanided tailings by utilizing a surface crystallization process of microcrystalline glass granules.
The vitrification solidification of the cyanide tailings is the best way to realize the harmless treatment of the cyanide tailings, the traditional vitrification solidification treatment mode is to melt the cyanide tailings at high temperature to form glass liquid, then directly carry out water quenching to form water quenched glass granules, an amorphous structure is formed due to the rapid cooling process of the high-temperature glass liquid, heavy metal elements in the cyanide tailings are solidified in the networks of the cyanide tailings, from the physical and chemical aspects, a non-static glass body is an intermediate stable intermediate compared with a crystal structure, and the stability of the solidification degree of the heavy metal is lower than that of the crystal structure. If the solidification of heavy metal in cyanidation tailings is realized by adopting a microcrystalline glass production route, the water-quenched glass granules or the formed plate needs to be subjected to secondary heat treatment, the heat treatment temperature can be up to 900 ℃ sometimes, more energy needs to be consumed, and the cost cannot be borne by a waste production enterprise. The invention utilizes a surface crystallization phenomenon in the production process of the microcrystalline glass to realize the solidification of heavy metal, the surface crystallization is a factor which seriously affects the performance of products in the production process of the microcrystalline glass and is needed to be avoided to the utmost extent in industrial production, but the invention just utilizes the phenomenon, compared with the traditional vitrification solidification means, a crystal shell is formed on the surface of glass particles after the surface crystallization, the interior of the crystal shell is still in an amorphous state, heavy metal elements in cyanidation tailings can be used as a phase forming component to form a new crystal phase in the crystal shell, heavy metal elements in an amorphous core are solidified in a glass grid of the amorphous core, and the surface crystallization is carried out spontaneously in the whole process, thereby greatly reducing the treatment cost. The obtained microcrystalline glass particles can be used for preparing novel cementing materials and filling aggregate for mine cemented filling, and have good economic, environmental and social benefits.
The cyaniding tailings in the invention comprise the following components in percentage by mass:
Na2O 0.5％～4.0％、MgO 0.4％～4.0％、Al2O3 8.5％～20.5％、SiO2 45.0％～70.0％、K2O 0.5％～3.0％、CaO 2.0％～6％、TiO2 0.1％～1.5％、Cr2O3 0.01％～0.5％、MnO 0.01％～1.5％、Fe2O3 0.5％～7.5％、CuO 0.01％～0.5％、ZnO 0.05％～0.6％、As2O30.01％～1.05％、SrO 0.01％～0.09％、ZrO2 0.01％～0.05％、Sb2O3 0.01％～0.3％、BaO 0.01％～0.5％、CeO20.01-0.09 percent, 0.01-0.55 percent of PbO and 2.0-6.0 percent of loss on ignition.
The microcrystalline particles for harmless treatment of cyanide tailings are prepared from decyanation tailings and auxiliary raw materials, wherein the decyanation tailings account for 40.0-60.0 wt% of the total weight of the raw materials, the auxiliary raw materials account for 35.0-55.0 wt% of the total weight of the raw materials, and the nucleating agent accounts for 0.5-5.0 wt% of the total weight of the raw materials; the auxiliary raw materials are as follows: quartz sand or Silica (SiO)2) Limestone or calcite (CaCO)3) Sodium carbonate (Na)2CO3) Fluorite (CaF)2) Alumina (Al)2O3) Potassium carbonate (K)2CO3) Magnesium oxide (MgO), sodium nitrate (NaNO)3) Three or more or all of them, the weight ratio of them is 30-60:0-10:5-15:0-5:3-9:0-5:5-10: 3-5; the nucleating agent is TiO2、ZnO、MnO、Cr2O3、Fe2O3And one or more or all of BaO, and the weight ratio of the BaO to the BaO is 0-3:0-5:0-2:0-3:0-4: 0-2.
A method for harmlessly treating cyaniding tailings in a crystallization process on the surfaces of microcrystalline glass granules comprises the following steps of firstly, conveying wet-based cyaniding tailings containing certain moisture to a rotary kiln for primary roasting, removing all moisture and partial cyanide components in the cyaniding tailings, and ensuring that the cyaniding tailings are always in a negative pressure state in the primary roasting process; and conveying the roasted cyaniding tailings to a roasting furnace for secondary roasting, wherein the cyaniding tailings are always in an oxygen-enriched state in the secondary roasting process, and removing all cyanides in the cyaniding tailings to obtain the decyanation tailings. And (2) conveying a basic batch prepared from decyanation tailings and auxiliary raw materials according to a ratio to a high-temperature melting furnace, melting the basic batch into uniform glass liquid at high temperature, conveying the glass liquid to a granulator for granulation, and shaping to obtain microcrystalline glass particles with a mantle structure. The method comprises the following specific steps:
(1) scattering: the water content of the cyanidation tailings after filter pressing and dehydration is generally less than or equal to 20 percent and is generally in a cake shape, and the cyanidation tailings are scattered into proper feed particle size by a scattering machine;
preferably, the particle size of the scattered feed is less than or equal to 30 mm.
(2) Primary roasting: conveying the scattered cyaniding tailings to a rotary kiln for primary roasting, ensuring that the whole primary roasting process is in a negative pressure state, and removing part of cyanides and all water in the cyaniding tailings;
preferably, the roasting temperature is 700-;
(3) secondary roasting: conveying the primarily roasted cyanidation tailings to a roasting kiln for secondary roasting, wherein during secondary roasting, the whole material is in a positive pressure and oxygen-enriched state, so that cyanide components are fully decomposed at high temperature, and the material is cooled to obtain decyanation tailings and conveyed to a stockyard for stockpiling;
preferably, the secondary roasting temperature is 400-800 ℃, and the time is 5-180 min;
(4) preparing materials: crushing the decyanation tailings to be less than or equal to 5mm by using a crusher, accurately weighing the materials according to a certain proportion, and then putting the materials into a mixer for full mixing to obtain a basic mixture, wherein the particle size of the auxiliary components is less than or equal to 2 mm;
(5) melting: putting the basic mixture into a glass melting furnace for high-temperature melting, wherein the melting temperature is 1400-1550 ℃, the melting time is 0.5-5.0 h, and the high-temperature melt is in a uniform and clear state;
preferably, the melting temperature of the high-temperature molten glass liquid is 1430-1500 ℃;
preferably, the melting time of the high-temperature molten glass liquid is 1.0-3.0 h.
(6) And (3) granulation: when the high-temperature molten glass flows out from the outlet of the melting furnace, cutting the glass melt into glass sections at high speed by using a heat-resistant cutter, and shaping the glass sections into spheres by using a shaping coil;
preferably, the size of the glass particles after granulation molding is 10-20 mm.
(7) Warehousing: the granulated and formed glass particles can automatically generate surface crystallization in the air to form microcrystalline glass particles with a mantle structure, the surface of the microcrystalline glass particles is a crystal shell, and the inner part of the microcrystalline glass particles is an amorphous core, and the microcrystalline glass particles are conveyed to a warehouse for storage.
The microcrystalline glass particles obtained by the cyanide tailings innocent treatment method can be used for preparing novel cementing materials and filling aggregate for mine cemented filling.
The invention has the following beneficial effects:
(1) the invention provides a method for harmlessly treating cyanide tailings in a crystallization process on the surface of microcrystalline glass granules, which removes cyanide through two-stage roasting, so that heavy metal in the cyanide tailings is solidified in microcrystalline glass particles prepared by high-temperature melting, and the solidification of the heavy metal in the cyanide tailings is realized.
(2) The decyanation tailings and the auxiliary raw materials are melted into glass liquid at high temperature, in the process of granulating and forming the glass liquid, as the temperature is reduced, nucleation components and energy fluctuation in a microcrystalline glass system enable microcrystalline glass particles to automatically generate a surface crystallization process in the air, and finally form 'mantle' type microcrystalline glass particles with crystal shells on the surfaces and amorphous cores inside, heavy metal elements in the cyanidation tailings serve as phase-forming components in the crystal shells to form new crystal phases, the heavy metal elements in the amorphous cores are solidified in glass grids, and the heavy metal elements in the crystal shells are very stable because the heavy metal elements in the crystal shells become the components of the crystal network structures. When the heavy metal elements solidified in the amorphous core are corroded outside the glass body, the solidified heavy metal elements in the amorphous core still have the possibility of being leached, and the crystal in the crystal shell has higher stability compared with the intermediate glass phase, so that a structure of a stable body coated metastable glass body is formed, and the structure has better effect on the solidification of heavy metal in cyanidation tailings compared with the ordinary vitrification solidification.
(3) The microcrystalline glass particles obtained by the invention undergo a rapid cooling process from a high-temperature molten mass to room temperature, although the outer surface layer is a crystal phase, the inner part of the microcrystalline glass particles is still an amorphous phase, the forming process is similar to the forming process of fly ash, blast furnace granulated slag, waste incineration fly ash and the like, the microcrystalline glass particles also have very high potential pozzolanic activity, can be used for replacing slag to be used as a novel cementing material for producing mine filling, finally realize the comprehensive utilization of cyanidation tailings, and have remarkable economic benefit, environmental benefit and social benefit.
(4) The leaching liquid concentration of main concerned elements in the prepared microcrystalline glass particles of the cyanided tailings treated by the method provided by the invention does not exceed the concentration limit value specified in GB 5085.3-2007 hazardous waste identification standard leaching toxicity identification, the pH does not exceed the standard limit value of GB 5085.1-2007 hazardous waste identification standard corrosivity identification, and the cyanided tailings do not have leaching toxicity and corrosivity any more.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a process for the harmless disposal and comprehensive utilization of cyanide tailings used in the embodiment of the present invention.
FIG. 2 is a schematic view of the structure of the "mantle" of the microcrystalline glass particles of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The method for harmlessly treating the cyanide tailings by utilizing the surface crystallization process of the microcrystalline glass granules comprises the following steps:
in some preferred embodiments of the present invention, the decyanation tailings comprise 40.0-60.0 wt.% of the total weight of the raw materials, the auxiliary raw materials comprise 35.0-55.0 wt.% of the total weight of the raw materials, and the nucleating agent comprises 0.5-5.0 wt.% of the total weight of the raw materials.
In some preferred embodiments of the present invention, the auxiliary raw material for matching with the decyanation tailings is quartz sand or Silica (SiO)2) Limestone or calcite (CaCO)3) Sodium carbonate (Na)2CO3) Fluorite (CaF)2) Alumina (Al)2O3) Potassium carbonate (K)2CO3) Magnesium oxide (MgO), sodium nitrate (NaNO)3) Three or more or all of them, the weight ratio of them is 30-60:0-10:5-15:0-5:3-9:0-5:5-10: 3-5; the nucleating agent is TiO2、ZnO、MnO、Cr2O3、Fe2O3And one or more or all of BaO, and the weight ratio of the BaO to the BaO is 0-3:0-5:0-2:0-3:0-4: 0-2.
The physicochemical properties of the added auxiliary raw materials are used as the fluxing agent of the decyanation tailings, and the melting property of the basic batch can be obviously improved within the proportion range.
The cyaniding tailings in the invention comprise the following components in percentage by mass:
Na2O 0.5％～4.0％、MgO 0.4％～4.0％、Al2O3 8.5％～20.5％、SiO2 45.0％～70.0％、K2O 0.5％～3.0％、CaO 2.0％～6％、TiO2 0.1％～1.5％、Cr2O3 0.01％～0.5％、MnO 0.01％～1.5％、Fe2O3 0.5％～7.5％、CuO 0.01％～0.5％、ZnO 0.05％～0.6％、As2O30.01％～1.05％、SrO 0.01％～0.09％、ZrO20.01％～0.05％、Sb2O3 0.01％～0.3％、BaO 0.01％～0.5％、CeO20.01-0.09 percent, 0.01-0.55 percent of PbO and 2.0-6.0 percent of loss on ignition.
In some preferred embodiments of the present invention, the glass particles are obtained by granulating and shaping a high-temperature molten glass liquid by a granulator.
In some preferred embodiments of the invention, the heating and melting temperature and time are preferably selected, and the heating and melting temperature is 1430-1500 ℃; the time for heating and high-temperature melting is 1.0-3.0 h.
In some preferred embodiments of the present invention, a device for heat melting is preferred, the heat melting being performed in a glass melting furnace.
In some preferred embodiments of the present invention, the glass particles are pelletized by cutting the glass melt into glass segments with a heat-resistant knife and shaping the glass segments into spheres with a shaping coil while the molten glass flows out of the outlet of the melting furnace.
In some preferred embodiments of the present invention, the size of the glass particles after the granulation molding is 10-20 mm.
The microcrystalline glass particles prepared by the invention can be used for preparing novel cementing materials and filling aggregate for mine cemented filling.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
And (3) smashing the cyanide tailings (the water content is 10%) after filter pressing and dehydration by using a smashing machine (the feed granularity is 20 mm).
And (3) conveying the scattered cyanided tailings to a rotary kiln, and performing primary roasting at 700 ℃ for 30min under negative pressure of-30 kpa to remove part of cyanides and all water in the cyanided tailings.
And conveying the primarily roasted cyanidation tailings to a roasting kiln for secondary roasting at 600 ℃ for 90min, wherein during secondary roasting, the material is in a positive pressure and oxygen-enriched state in the whole process, so that cyanide components are fully decomposed at high temperature, and the material is cooled to obtain decyanation tailings and conveyed to a stockyard for stockpiling.
Crushing decyanation tailings to 3mm by using a crusher, wherein the particle size of the auxiliary component is 2mm, the decyanation tailings account for 40.0 wt% of the total weight of the raw materials, the auxiliary raw materials account for 35.0 wt% of the total weight of the raw materials, and the nucleating agent accounts for 0.5 wt% of the total weight of the raw materials, accurately weighing the materials according to the proportion, and then putting the materials into a mixer for fully mixing to obtain a basic mixture.
And putting the basic mixture into a glass melting furnace for high-temperature melting, wherein the melting temperature is 1500 ℃, the melting time is 3.0h, and the high-temperature melt is in a uniform and clear state.
When the high-temperature molten glass flows out from the outlet of the melting furnace, the glass melt is cut into glass sections at high speed by a heat-resistant cutter, the glass sections are shaped into spheres by a shaping coil, and the size of the glass particles after granulation molding is 15 mm.
The granulated and formed glass particles can automatically generate surface crystallization in the air to form microcrystalline glass particles with a mantle structure, the surface of the microcrystalline glass particles is a crystal shell, and the inner part of the microcrystalline glass particles is an amorphous core, and the microcrystalline glass particles are conveyed to a warehouse for storage.
The leaching solution concentration of main concern elements in the prepared microcrystalline glass particles does not exceed the concentration limit value specified by the national standard GB 5085.3-2007 Standard for identifying hazardous waste Leaching toxicity identification, the pH value does not exceed the Standard limit value GB 5085.1-2007 Standard for identifying hazardous waste corrosivity identification, and the microcrystalline glass particles do not have leaching toxicity and corrosivity any more.
Example 2
And (3) smashing the cyanide tailings (the water content is 15%) after filter pressing and dehydration by using a smashing machine (the feed granularity is 15 mm).
And (3) conveying the scattered cyanidation tailings to a rotary kiln for primary roasting at 750 ℃ for 40min under negative pressure of-40 kpa, and removing part of cyanides and all water in the cyanidation tailings.
And conveying the primarily roasted cyanidation tailings to a roasting kiln for secondary roasting at the roasting temperature of 500 ℃ for 100min, wherein the material is in a positive pressure and oxygen-enriched state in the whole process during secondary roasting, so that cyanide components are fully decomposed at high temperature, and the material is cooled to obtain decyanation tailings and conveyed to a stockyard for stockpiling.
Crushing decyanation tailings to 4mm by using a crusher, wherein the particle size of the auxiliary component is 1mm, the decyanation tailings account for 50.0 wt% of the total weight of the raw materials, the auxiliary raw materials account for 40.0 wt% of the total weight of the raw materials, and the nucleating agent accounts for 2.0 wt% of the total weight of the raw materials, accurately weighing the materials according to the proportion, and then putting the materials into a mixer for fully mixing to obtain a basic mixture.
And putting the basic mixture into a glass melting furnace for high-temperature melting, wherein the melting temperature is 1430 ℃, the melting time is 2.0h, and the high-temperature melt is in a uniform and clear state.
When the high-temperature molten glass flows out from the outlet of the melting furnace, the glass melt is cut into glass sections at high speed by a heat-resistant cutter, the glass sections are shaped into spheres by a shaping coil, and the size of the glass particles after granulation molding is 10 mm.
The granulated and formed glass particles can automatically generate surface crystallization in the air to form microcrystalline glass particles with a mantle structure, the surface of the microcrystalline glass particles is a crystal shell, and the inner part of the microcrystalline glass particles is an amorphous core, and the microcrystalline glass particles are conveyed to a warehouse for storage.
The leaching solution concentration of main concern elements in the prepared microcrystalline glass particles does not exceed the concentration limit value specified by the national standard GB 5085.3-2007 Standard for identifying hazardous waste Leaching toxicity identification, the pH value does not exceed the Standard limit value GB 5085.1-2007 Standard for identifying hazardous waste corrosivity identification, and the microcrystalline glass particles do not have leaching toxicity and corrosivity any more.
Example 3
And (3) smashing the cyanide tailings (the water content is 20%) subjected to filter pressing and dehydration by using a smashing machine (the feed granularity is 30 mm).
And (3) conveying the scattered cyanided tailings to a rotary kiln for primary roasting at 800 ℃ for 60min under negative pressure of-60 kpa, and removing part of cyanides and all water in the cyanided tailings.
And conveying the primarily roasted cyanidation tailings to a roasting kiln for secondary roasting at 800 ℃ for 180min, wherein during secondary roasting, the material is in a positive pressure and oxygen-enriched state in the whole process, so that cyanide components are fully decomposed at high temperature, and the material is cooled to obtain decyanation tailings and conveyed to a stockyard for stockpiling.
Crushing decyanation tailings to 4mm by using a crusher, wherein the particle size of the auxiliary component is 1mm, the decyanation tailings account for 55.0 wt% of the total weight of the raw materials, the auxiliary raw materials account for 55.0 wt% of the total weight of the raw materials, and the nucleating agent accounts for 5.0 wt% of the total weight of the raw materials, accurately weighing the materials according to the proportion, and then putting the materials into a mixer for fully mixing to obtain a basic mixture.
And putting the basic mixture into a glass melting furnace for high-temperature melting, wherein the melting temperature is 1550 ℃, the melting time is 3.0h, and the high-temperature melt is in a uniform and clear state.
When the high-temperature molten glass flows out from the outlet of the melting furnace, the glass melt is cut into glass sections at high speed by a heat-resistant cutter, the glass sections are shaped into spheres by a shaping coil, and the size of the glass particles after granulation molding is 20 mm.
The granulated and formed glass particles can automatically generate surface crystallization in the air to form microcrystalline glass particles with a mantle structure, the surface of the microcrystalline glass particles is a crystal shell, and the inner part of the microcrystalline glass particles is an amorphous core, and the microcrystalline glass particles are conveyed to a warehouse for storage.
The leaching solution concentration of main concern elements in the prepared microcrystalline glass particles does not exceed the concentration limit value specified by the national standard GB 5085.3-2007 Standard for identifying hazardous waste Leaching toxicity identification, the pH value does not exceed the Standard limit value GB 5085.1-2007 Standard for identifying hazardous waste corrosivity identification, and the microcrystalline glass particles do not have leaching toxicity and corrosivity any more.
Example 4
And (3) smashing the cyanide tailings (the water content is 16%) subjected to filter pressing and dehydration by using a smashing machine (the feed granularity is 23 mm).
And (3) conveying the scattered cyanided tailings to a rotary kiln for primary roasting at 760 ℃, for 50min and under negative pressure of-50 kpa, and removing part of cyanides and all water in the cyanided tailings.
And conveying the primarily roasted cyanidation tailings to a roasting kiln for secondary roasting at 700 ℃ for 120min, wherein during secondary roasting, the material is in a positive pressure and oxygen-enriched state in the whole process, so that cyanide components are fully decomposed at high temperature, and the material is cooled to obtain decyanation tailings and conveyed to a stockyard for stockpiling.
Crushing decyanation tailings to 3mm by using a crusher, wherein the particle size of the auxiliary component is 1mm, the decyanation tailings account for 45.0 wt% of the total weight of the raw materials, the auxiliary raw materials account for 40.0 wt% of the total weight of the raw materials, and the nucleating agent accounts for 4.0 wt% of the total weight of the raw materials, accurately weighing the materials according to the proportion, and then putting the materials into a mixer for fully mixing to obtain a basic mixture.
And putting the basic mixture into a glass melting furnace for high-temperature melting, wherein the melting temperature is 1450 ℃, the melting time is 2.5 hours, and the high-temperature melt is in a uniform and clear state.
When the high-temperature molten glass flows out from the outlet of the melting furnace, the glass melt is cut into glass sections at high speed by a heat-resistant cutter, the glass sections are shaped into spheres by a shaping coil, and the size of the glass particles after granulation molding is 18 mm.
The granulated and formed glass particles can automatically generate surface crystallization in the air to form microcrystalline glass particles with a mantle structure, the surface of the microcrystalline glass particles is a crystal shell, and the inner part of the microcrystalline glass particles is an amorphous core, and the microcrystalline glass particles are conveyed to a warehouse for storage.
The leaching solution concentration of main concern elements in the prepared microcrystalline glass particles does not exceed the concentration limit value specified by the national standard GB 5085.3-2007 Standard for identifying hazardous waste Leaching toxicity identification, the pH value does not exceed the Standard limit value GB 5085.1-2007 Standard for identifying hazardous waste corrosivity identification, and the microcrystalline glass particles do not have leaching toxicity and corrosivity any more.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (10)
1. The method for harmlessly treating the cyanide tailings by utilizing the surface crystallization process of the microcrystalline glass granules is characterized by comprising the following steps of:
conveying wet-based cyanidation tailings to a rotary kiln for primary roasting to remove all water and partial cyanide components in the cyanidation tailings, wherein the cyanidation tailings are always in a negative pressure state in the primary roasting process;
conveying the roasted cyaniding tailings to a roasting furnace for secondary roasting, wherein the cyaniding tailings are always in an oxygen-enriched state in the secondary roasting process, and removing all cyanides in the cyaniding tailings to obtain decyanation tailings;
and (3) conveying a basic batch prepared from decyanation tailings and auxiliary raw materials according to a ratio to a high-temperature melting furnace, melting the basic batch into uniform glass liquid at high temperature, conveying the high-temperature molten glass liquid to a granulator for granulation, and shaping to obtain microcrystalline glass particles with a mantle structure.
2. The method according to claim 1, wherein the cyanidation tailings comprise the following components in mass percent:
Na2O 0.5％～4.0％、MgO 0.4％～4.0％、Al2O3 8.5％～20.5％、SiO245.0％～70.0％、K2O 0.5％～3.0％、CaO 2.0％～6％、TiO2 0.1％～1.5％、Cr2O30.01％～0.5％、MnO 0.01％～1.5％、Fe2O3 0.5％～7.5％、CuO 0.01％～0.5％、ZnO 0.05％～0.6％、As2O30.01％～1.05％、SrO 0.01％～0.09％、ZrO2 0.01％～0.05％、Sb2O3 0.01％～0.3％、BaO 0.01％～0.5％、CeO2 0.01％～0.09％、PbO 0.01％～0.55％。
3. the method as claimed in claim 1, wherein the first-stage roasting temperature is 700-800 ℃ and the roasting time is 5-60 min; in the secondary roasting process, the roasting temperature is 400-800 ℃, and the time is 5-180 min.
4. The method according to claim 1, wherein the glass-ceramic particles are prepared from decyanation tailings and auxiliary raw materials, wherein the decyanation tailings account for 40.0-60.0 wt.% of the total weight of the raw materials, the auxiliary raw materials account for 35.0-55.0 wt.% of the total weight of the raw materials, and the nucleating agent accounts for 0.5-5.0 wt.% of the total weight of the raw materials;
the auxiliary raw materials are selected from: SiO 22、CaCO3、Na2CO3、CaF2、Al2O3Potassium carbonate K2CO3、MgO、NaNO3Three or more than three materials;
the nucleating agent is selected from: TiO 22、ZnO、MnO、Cr2O3、Fe2O3And BaO.
5. The method according to claim 1, wherein the microcrystalline glass particles are obtained by granulating and shaping a high-temperature molten glass liquid by a granulator;
the melting temperature of the high-temperature molten glass liquid is 1430-1500 ℃;
the melting time of the high-temperature molten glass liquid is 1.0-3.0 h.
6. The method according to claim 1, wherein the glass-ceramic particles are granulated by cutting the glass melt into glass segments by a heat-resistant knife and shaping the glass segments into spheres by a shaping coil when the high-temperature molten glass flows out of the outlet of the melting furnace.
7. The method according to claim 1, wherein the glass particles after the granulation molding have a size of 10 to 20 mm.
8. The method as claimed in claim 1, wherein the glass particles after granulation molding are subjected to surface crystallization in air to form microcrystalline glass particles with a mantle structure, wherein the surface of the microcrystalline glass particles is a crystalline shell and the interior of the microcrystalline glass particles is an amorphous core.
9. The method according to claim 1, wherein the cyanide tailings microcrystalline glass particles can be used for preparing novel cementing materials and filling aggregate for mine cemented filling.
10. Method according to claim 1, characterized in that it comprises the following steps:
step (1), scattering: the water content of the cyanidation tailings after filter pressing and dehydration is generally less than or equal to 20 percent and is generally in a cake shape, and the cyanidation tailings are scattered into proper feed particle size by a scattering machine;
preferably, the granularity of the scattered feed is less than or equal to 30 mm;
step (2), primary roasting: conveying the scattered cyaniding tailings to a rotary kiln for primary roasting, ensuring that the whole primary roasting process is in a negative pressure state, and removing part of cyanides and all water in the cyaniding tailings;
preferably, the roasting temperature is 700-;
step (3), secondary roasting: conveying the primarily roasted cyanidation tailings to a roasting kiln for secondary roasting, wherein during secondary roasting, the whole material is in a positive pressure and oxygen-enriched state, so that cyanide components are fully decomposed at high temperature, and the material is cooled to obtain decyanation tailings and conveyed to a stockyard for stockpiling;
preferably, the secondary roasting temperature is 400-800 ℃, and the time is 5-180 min;
step (4) batching: crushing the decyanation tailings to be less than or equal to 5mm by using a crusher, accurately weighing the materials according to the proportion, and then putting the materials into a mixer for full mixing to obtain a basic mixture, wherein the particle size of the auxiliary components is less than or equal to 2 mm;
melting in step (5): putting the basic mixture into a glass melting furnace for high-temperature melting, wherein the melting temperature is 1400-1550 ℃, the melting time is 0.5-5.0 h, and the high-temperature melt is in a uniform and clear state;
preferably, the melting temperature of the high-temperature molten glass liquid is 1430-1500 ℃;
preferably, the melting time of the high-temperature molten glass liquid is 1.0-3.0 h;
and (6) granulating: when the high-temperature molten glass flows out from the outlet of the melting furnace, cutting the glass melt into glass sections at high speed by using a heat-resistant cutter, and shaping the glass sections into spheres by using a shaping coil;
preferably, the size of the glass particles after granulation molding is 10-20 mm;
step (7) warehousing: the glass particles after granulation and forming can automatically generate surface crystallization in the air to form microcrystalline glass particles with a mantle structure, the surface of which is a crystal shell and the interior of which is an amorphous core, and the microcrystalline glass particles are conveyed to a warehouse for storage.
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| CN114804676A (en) * | 2022-05-11 | 2022-07-29 | 北京金隅红树林环保技术有限责任公司 | Cement active mixed material prepared from waste incineration fly ash and cyanided tailings and preparation method thereof |
| CN115105783A (en) * | 2022-07-06 | 2022-09-27 | 中南大学 | Method for synchronously harmless recycling of waste incineration fly ash and cyanidation tailings |
| CN115672938A (en) * | 2022-10-28 | 2023-02-03 | 中国科学院过程工程研究所 | Method for synchronously and stably curing multiple heavy metals by core-shell structure glass curing body |
| GB2622256A (en) * | 2022-09-08 | 2024-03-13 | Corning Inc | Glass-ceramic articles and methods of making them |
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| CN115672938A (en) * | 2022-10-28 | 2023-02-03 | 中国科学院过程工程研究所 | Method for synchronously and stably curing multiple heavy metals by core-shell structure glass curing body |
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| ZA202108355B (en) | 2022-01-26 |
| CN112390526B (en) | 2022-10-28 |
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