Method for solidifying arsenic-containing material and co-processing copper smelting slag and application thereof

Abstract

The invention discloses a method for solidifying arsenic-containing materials and co-processing copper smelting slag and application of the method, and belongs to the technical field of metallurgical solid waste recycling and hazardous waste treatment. The method comprises the following steps: pretreating an arsenic-containing mixed material to obtain pretreated clinker; the arsenic-containing mixed material comprises an arsenic-containing material, a calcium-silicon additive and a modifier; mixing the pretreated clinker with molten copper smelting slag, and carrying out heat preservation treatment to obtain a vitrified melt; the temperature of the molten copper smelting slag ranges from 1250 DEG C to 1350 DEG C; and cooling the vitrification melt to obtain the arsenic-containing glass solidified body. According to the solidified body obtained through the method, the arsenic element is firmly solidified in a glass network structure, the leaching toxicity is low, the long-term stability is excellent, the problems that a traditional solidification method for arsenic-containing waste is poor in stability and prone to causing secondary pollution are effectively solved, and remarkable environmental benefits and economic benefits are achieved.

Description

Technical Field

[0001] This invention belongs to the field of arsenic-containing solid waste treatment technology, specifically relating to a method for solidifying arsenic-containing materials and co-processing copper smelting slag, and its application. Background Technology

[0002] Arsenic is a common associated element in major non-ferrous metal ores (such as copper, lead, and zinc). Statistics show that associated arsenic mineral resources account for as much as 87.1% of my country's total arsenic resources, indicating significant reserves. During non-ferrous metal smelting, arsenic in the ores enters various byproducts along with the smelting process. Taking the copper smelting industry as an example, the amount of hazardous waste generated annually, such as arsenic-containing flue dust and high-arsenic waste acid, poses a serious threat to soil, groundwater, and human health if improperly stored and disposed of. Therefore, the safe, stable, and harmless disposal of arsenic-containing hazardous waste is an urgent need in the field of environmental protection.

[0003] Currently, the main treatment approaches for arsenic-containing waste residue are divided into two categories: resource utilization and stabilization / solidification disposal. Resource utilization aims to extract arsenic and prepare arsenic products through pyrometallurgical or hydrometallurgical processes. However, due to the extreme toxicity of arsenic and its compounds, the market for these products is limited, and the extraction process itself poses a risk of secondary pollution, hindering the development and application of this approach. Therefore, solidification / stabilization technology, which stabilizes arsenic in an inert matrix, has become the mainstream direction for the disposal of arsenic-containing hazardous waste.

[0004] However, existing common curing / stabilization technologies still have significant drawbacks, making it difficult to simultaneously meet the core requirements of long-term stability and volume reduction. Specifically, cement curing: the process is simple, but it introduces a large amount of water and cementitious materials into the system, resulting in a significant increase in the volume of the cured body (high volume increase ratio). Furthermore, arsenic in the cement pores is easily corroded by acidic environments and re-leached out, leading to insufficient long-term stability. Ferric / calcium salt precipitation: This method converts arsenic into insoluble compounds through chemical precipitation. Although the precipitate formed by this method is small in volume, its chemical stability is greatly affected by the environmental pH value. Under natural weathering or acid rain conditions, it may transform, leading to the re-release of arsenic and posing a long-term safety risk.

[0005] Therefore, it is crucial to develop a arsenic-containing waste treatment technology that can achieve highly stable solidification. Summary of the Invention

[0006] To address the technical problems of poor long-term stability and easy leaching leading to secondary pollution in the solidification and treatment of arsenic-containing materials in the aforementioned commonly used technologies, this invention provides a method for solidifying arsenic-containing materials and co-treating copper smelting slag, comprising the following steps: Pre-treatment of an arsenic-containing mixture yields pre-treated clinker; the arsenic-containing mixture includes arsenic-containing materials, calcium-silicon additives, and modifiers. The pretreated clinker is mixed with molten copper smelting slag and then subjected to heat treatment to obtain a vitrified melt; the temperature of the molten copper smelting slag is 1250-1350℃. The vitrified melt is cooled to obtain an arsenic-containing glass solidified body.

[0007] Furthermore, the composition of the arsenic-containing mixture includes arsenic-containing materials, calcium-silicon additives, and modifiers in a mass ratio of 0.5-1:0.3-0.6:0.2-0.4.

[0008] Furthermore, the amount of arsenic-containing material added is 0.5-1t / 20t of smelting slag; the amount of calcium-silicon additive added is 0.3-0.6t / 20t of smelting slag; and the amount of the modifier added is 5-20kg / t of smelting slag.

[0009] Furthermore, the calcium-silicon additive comprises calcium oxide and silicon oxide, and the calcium-silicon ratio of the calcium-silicon additive is 1:2.5-5; The modified agent includes anhydrous sodium borate.

[0010] Furthermore, the pretreatment includes: granulating the arsenic-containing material to obtain an arsenic-containing precursor; and mixing the arsenic-containing precursor with the calcium-silicon additive and the modifier to obtain the pretreated clinker.

[0011] Furthermore, by mass fraction, the composition of the arsenic-containing material includes, but is not limited to: As 10-20%, Cu 8-15%, Pb 15-22%, S 0-8%, Si 0-2%, Fe 0-8%, with the remainder being oxygen and other unavoidable impurity elements.

[0012] Furthermore, the main phases in the molten copper smelting slag include iron(II,III) oxide and / or ferrous silicate; by mass fraction, the elemental composition of the molten copper smelting slag includes: Si 10-20%, Fe 40-50%, Ca 1-5%, Al 1-5%, Zn 0.5-3%, O 20-50%, with the remainder being unavoidable impurity elements.

[0013] Furthermore, the temperature of the heat preservation treatment is 1250-1350℃, and the duration of the heat preservation treatment is 30-60 minutes; The cooling process includes air cooling and water cooling, wherein the air cooling duration is 24-48 hours and the water cooling duration is 48-72 hours.

[0014] Furthermore, the arsenic leaching concentration of the arsenic-containing glass curing body is less than 0.5 mg / L; the arsenic element in the arsenic-containing glass curing body exists in the form of an amorphous glass phase.

[0015] This invention provides an application of the method for solidifying arsenic-containing materials and co-processing copper smelting slag as described in any of the above-mentioned methods in the treatment of arsenic-containing materials.

[0016] Compared with the prior art, the present invention has at least the following advantages: This invention provides a method for solidifying arsenic-containing materials and co-processing copper smelting slag. Through the synergistic effect of three core processes, it specifically solves the technical problems of poor long-term stability and easy leaching leading to secondary pollution in the solidification and treatment of arsenic-containing materials, and produces the following significant synergistic effects: Achieving long-term, efficient stabilization of arsenic and fundamentally blocking pollution risks: By pretreating arsenic-containing mixtures to form "pretreated clinker," the high-temperature reaction performance of the materials is effectively optimized. When the "pretreated clinker" is mixed with high-temperature "molten copper smelting slag," under the superior thermodynamic conditions provided by the slag, the highly toxic arsenate substances are completely destroyed and reconstructed, and the arsenic element is firmly embedded in the newly formed silicate glass network through chemical bonding.

[0017] The "vitrified melt" undergoes further optimized "heat preservation" and "cooling" processes to ultimately form a dense and homogeneous "arsenic-containing glass solidified body." This solidified body possesses extremely low permeability and chemical inertness, fundamentally altering the occurrence form of arsenic. This significantly suppresses its leaching toxicity and migration under natural environmental conditions (including acid, alkali, and groundwater erosion), thereby achieving long-term, safe storage of arsenic and eliminating the risk of secondary pollution.

[0018] This innovative collaborative treatment model combines energy conservation and waste resource utilization: It creatively integrates the treatment of arsenic-containing hazardous waste (such as arsenic flue dust) with the processing of copper smelting solid waste (molten copper smelting slag). The key technology lies in directly utilizing the molten copper smelting slag discharged from the side-blown furnace as the high-temperature reaction medium and main heat source, eliminating the need for a separate molten system for vitrification and achieving significant energy conservation and consumption reduction.

[0019] Meanwhile, the silicon, calcium, iron and other oxides in the molten copper slag itself provide the basic framework components for the formation of the glass network. Together with the "calcium silicon additive" and the "modifier", they work synergistically to build a stable matrix, thereby reducing the need for additional additives and realizing the in-situ efficient and comprehensive utilization of waste resources.

[0020] In summary, this invention successfully transforms arsenic-containing hazardous waste into a chemically stable glass-cured body with significant volume reduction through an innovative process chain of "pretreatment optimization—high-temperature synergistic melting—controllable curing." It overcomes the bottleneck of poor stability in traditional curing technologies at the fundamental level, achieves synergy in energy saving, consumption reduction, and resource utilization at the process level, and ultimately achieves a balance between environmental safety, technical economy, and engineering feasibility in its application. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0022] Figure 1 The image shows the XRD pattern of the arsenic-containing flue dust used in Example 1 of this invention. Figure 2 The image shows the XRD pattern of the molten copper smelting slag used in Example 1 of this invention. Figure 3 The image shown is the XRD pattern of the arsenic-containing glass-cured body prepared in Example 1 of this invention. Figure 4 This is a photograph of the edge portion of the arsenic-containing glass curing body prepared in Example 1 of the present invention; Figure 5 This is a photograph of the edge portion of the arsenic-containing glass curing body prepared in Comparative Example 4 of the present invention. Detailed Implementation

[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Furthermore, the technical solutions of the various embodiments of the present invention can be combined with each other, but only if they are based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0025] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention, as well as the prior art known to those skilled in the art and the description of the invention, may be implemented using any prior art methods, devices, and materials similar to or equivalent to the methods, devices, and materials in the embodiments of the present invention.

[0026] This invention provides a method for solidifying arsenic-containing materials and co-processing copper smelting slag, comprising the following steps: S1. Pre-treat the arsenic-containing mixture to obtain pre-treated clinker; the arsenic-containing mixture includes arsenic-containing materials, calcium-silicon additives, and modifiers.

[0027] In this invention, the arsenic-containing mixture comprises arsenic-containing materials, calcium-silicon additives, and a modifier in a mass ratio of 0.5-1:0.3-0.6:0.2-0.4. By precisely controlling the proportions of the arsenic-containing materials, calcium-silicon additives (with a specific Ca / Si ratio), and the modifier (anhydrous sodium borate), this invention not only technically ensures the melting temperature, fluidity, and stability of the final solidified body, but also reduces the amount of additives used and lowers costs.

[0028] In some embodiments of the present invention, the amount of arsenic-containing material added is 0.5-1t / 20t smelting slag; the amount of calcium-silicon additive added is 0.3-0.6t / 20t smelting slag; and the amount of the modifier added is 5-20kg / t smelting slag.

[0029] In this invention, the composition of the arsenic-containing material, by mass fraction, includes, but is not limited to: As 10-20%, Cu 8-15%, Pb 15-22%, S 0-8%, Si 0-2%, Fe 0-8%, with the remainder being oxygen and other unavoidable impurity elements.

[0030] In some embodiments of the present invention, the arsenic content in the arsenic-containing material may be 10-15%, 10-18%, 12-20%, or 15-20%; in some embodiments, the lead content in the arsenic-containing material may be 16-22%, 17-22%, or 18-22%; in some embodiments, the copper content in the arsenic-containing material may be 10-15%, 9-15%, 10-14%, or 9-14%; in some embodiments, the sulfur content in the arsenic-containing material may be 1-8%, 2-8%, 3-8%, 1-7%, 2-7%, or 3-7%.

[0031] In some embodiments of the present invention, the arsenic-containing material is arsenic-containing solid waste.

[0032] In some embodiments of the present invention, the main component of the arsenic-containing material may be an arsenate phase, which is prone to volatilization at high temperatures.

[0033] For example, the arsenic-containing material may be arsenic flue dust.

[0034] In some embodiments of the present invention, the calcium-silicon additive comprises calcium oxide and silicon oxide, and the calcium-silicon ratio of the calcium-silicon additive is 1:2.5-5. Exemplarily, the calcium-silicon ratio of the calcium-silicon additive may be 1:2.5-4, 1:2.5-3, 1:3-5, or 1:3-4.

[0035] The calcium-silicon additive is used to form a stable silicate glass network structure under molten conditions.

[0036] In some embodiments of the present invention, the modifier comprises anhydrous sodium borate, which is used to improve melt flowability, reduce melting temperature and enhance the solidification stability of arsenic.

[0037] In this invention, the pretreatment includes: granulating the arsenic-containing material to obtain an arsenic-containing precursor; and mixing the arsenic-containing precursor with the calcium-silicon additive and the modifier to obtain the pretreated clinker.

[0038] The purpose of the granulation process is to prevent arsenic from volatilizing under subsequent high-temperature conditions. This invention granulates arsenic-containing materials to form granular arsenic-containing precursor materials with a certain mechanical strength.

[0039] In some embodiments, the particle size of the arsenic-containing precursor can be 1-5 mm.

[0040] In some embodiments, the granulated arsenic-containing material can be mixed with calcium-silicon additives and modifiers in a set ratio to ensure uniform dispersion of each component and guarantee the stability of the glass transition reaction between the pretreated clinker and the molten copper smelting slag.

[0041] For example, the granulated arsenic-containing material can be mixed evenly with calcium-silicon additives and modifiers in the above proportions in a closed mixer for a mixing time of not less than 30 minutes.

[0042] In this invention, pre-treated clinker can be fed into a chute storage bin via a closed conveying method to avoid dust generation and ensure the airtightness and safety of the entire feeding process.

[0043] S2. The pretreated clinker is mixed with molten copper smelting slag and then subjected to heat treatment to obtain a vitrified melt; the temperature of the molten copper smelting slag is 1250-1350℃.

[0044] In this invention, the main phases in the molten copper smelting slag include iron(II,III) oxide and / or ferrous silicate.

[0045] In some embodiments, the elemental composition of the molten copper smelting slag, by mass fraction, includes: Si 10-20%, Fe 40-50%, Ca 1-5%, Al 1-5%, Zn 0.5-3%, O 20-50%, with the remainder being unavoidable impurity elements. Here, Fe refers to the iron element in ferric oxide and ferrous oxide.

[0046] This invention innovatively combines two types of waste generated during copper smelting: side-blown furnace smelting slag and arsenic flue dust. The residual heat of the high-temperature smelting slag serves as a partial energy source for the vitrification of the arsenic flue dust, while the smelting slag itself provides the basic silicon and calcium components for glass formation. This reduces the consumption of additional additives, achieving efficient and comprehensive utilization of waste resources, thus combining economic and environmental benefits.

[0047] In some embodiments, mixing the pretreated clinker with molten copper smelting slag to obtain a vitrified melt may include the following steps: S21. The pretreated clinker is placed in a chute and fed into the slag bag; This invention employs a high-temperature resistant chute for continuous and stable feeding of the mixture. By controlling the chute's inclination angle, the mixture enters the pre-arranged slag bags at a stable flow rate; preferably, the chute is kept in a closed or semi-closed state to prevent dust from escaping.

[0048] It should be noted that the capacity of the slag bag should match the single batch processing volume, usually filled to 80%-90% of its volume, to avoid underfilling or overfilling affecting the subsequent melting reaction and heat transfer process.

[0049] S22. The molten copper slag discharged from the smelting furnace is discharged into the slag bag.

[0050] In some embodiments, the smelting furnace includes a side-blown furnace; In some more specific embodiments, step S22 may include: directing the high-temperature molten copper slag (temperature 1250-1350°C) from the outlet of the side-blown smelting furnace into a connected refractory chute through the slag outlet on the side of the furnace body.

[0051] For example, the opening of the slag outlet and the inclination angle of the chute (usually 25-40°) can be controlled to allow the melt to flow smoothly and continuously into the slag pot arranged below, utilizing its own gravity and fluidity.

[0052] It should be noted that the slag bag should be constructed with a heavy steel shell lined with refractory material to have sufficient thermal stability to withstand the thermal shock of high-temperature molten slag.

[0053] It should also be noted that during the slag removal process, the flow rate and volume of the molten slag must be controlled to avoid slag splashing or overfilling of the molten material in the slag pot. The amount of molten material loaded at one time should generally not exceed 85% of the slag pot volume, so as to reserve operating space for subsequent possible reheating, stirring or addition of other components.

[0054] S23. After slag removal, let the slag bag stand still to allow the molten slag to settle and homogenize naturally within the bag. Utilize the high temperature of the molten copper slag to cause the arsenic-containing materials and additives to undergo a melting reaction. Control the melting temperature within the range of 1250-1350℃ and hold for no less than 30 minutes to ensure the full formation of the glass phase and the formation of a glassy melt.

[0055] In this invention, the temperature of the heat preservation treatment is 1250-1350℃, and the duration of the heat preservation treatment is 30-60 minutes.

[0056] The heat preservation process is a high-temperature melting and vitrification process that firmly solidifies highly toxic arsenate substances in a chemically stable silicate glass network. This fundamentally changes the occurrence form of arsenic, greatly reduces its leaching toxicity and migration under natural conditions, effectively blocks the environmental pollution pathway, and solves the problem of treating arsenic-containing hazardous waste.

[0057] S3. The vitrified melt is cooled to obtain an arsenic-containing glass solidified body.

[0058] The cooling process includes air cooling and water cooling, wherein the air cooling duration is 24-48 hours and the water cooling duration is 48-72 hours. The air cooling stage utilizes air convection to remove heat, causing the slag to initially solidify and release some thermal stress, forming a preliminarily stable solid shell. The water cooling stage further stabilizes the internal structure of the slag through rapid cooling, ensuring that harmful substances such as arsenic are fully solidified within the glassy matrix, effectively inhibiting their subsequent leaching.

[0059] This invention effectively avoids internal stress cracking of the glass body caused by rapid cooling by setting a cooling regime of (air cooling for 24-48 h + water cooling for 48-72 h), ensuring the long-term integrity of the solidified body and preventing secondary contamination. At the same time, the optimized design of this cooling regime also ensures that the high-temperature melt can form a uniform, dense and high-gloss stable glass phase structure, thereby maximizing the curing effect of vitrification on arsenic.

[0060] In some embodiments, slag ladles containing insulated vitrified melt can be safely transported to a designated slow cooling area using a dedicated slag ladle truck for cooling. During transport, the slag ladles must be kept stable to prevent violent shaking that could cause molten slag to splash out. Upon arrival at the slow cooling area, the slag ladles should be neatly placed in a dedicated area with good ventilation and drainage, ensuring sufficient spacing between slag ladles (ideally no less than 1.5 meters) to guarantee airflow and safety for subsequent operations.

[0061] In some embodiments, the air cooling can be carried out under ambient atmospheric conditions.

[0062] In some embodiments, water cooling may include: starting a spray system or using a crane to lift the slag bag into a water cooling pool, continuously and uniformly spraying cooling water onto the surface of the slag bag, or completely immersing the slag bag in circulating cooling water for forced water cooling.

[0063] In this invention, the arsenic leaching concentration of the arsenic-containing glass curing body is less than 0.5 mg / L; the arsenic element in the arsenic-containing glass curing body exists in the form of an amorphous glass phase.

[0064] The present invention also provides an application of the method for solidifying arsenic-containing materials and co-processing copper smelting slag as described in any of the above claims in the treatment of arsenic-containing materials.

[0065] To facilitate a further understanding of the present invention by those skilled in the art, the following examples are provided: Example 1 This embodiment provides a method for solidifying arsenic-containing materials and co-processing copper smelting slag, the steps of which are as follows: S1. Pre-treat the arsenic-containing mixture to obtain pre-treated clinker; the arsenic-containing mixture consists of arsenic-containing material, calcium-silicon additive, and modifier; based on the treatment of 20 tons of copper smelting slag, the amount of arsenic-containing material added is 1 ton, the amount of calcium-silicon additive added is 0.3 tons, and the amount of modifier added is 15 kg per ton of smelting slag.

[0066] Specifically: The arsenic-containing material is granulated to obtain an arsenic-containing precursor; the particle size after granulation is controlled at 1-5 mm to reduce its volatilization at high temperatures. The arsenic-containing precursor is mixed with calcium-silicon additives and modifiers in a closed mixer in proportion, and the mixing time is not less than 30 minutes to ensure uniform material distribution, thus obtaining pretreated clinker.

[0067] Arsenic-containing materials: These were taken from arsenic-containing flue dust produced by a large copper smelter in Yunnan (its elemental analysis is shown in Table 1). Figure 1 The XRD pattern of the arsenic-containing flue dust used in Example 1 of this invention shows that the main phases in the arsenic flue dust are arsenates.

[0068] Table 1. Elemental analysis (wt%) of arsenic-containing fumigant Calcium-silicon additive: Industrial-grade calcium oxide and silicon oxide are mixed at a calcium-silicon ratio (Ca / Si) of 1:3 to obtain a calcium-silicon additive.

[0069] Modified agent: Take industrial anhydrous sodium borate (Na2B4O7, modified agent), with a purity ≥95%.

[0070] Among them, calcium oxide (CaO), silicon dioxide (SiO2), and industrial anhydrous sodium borate (Na2B4O7) were all purchased from Aladdin (Reagent) Shanghai Co., Ltd.

[0071] S2. The pretreated clinker is mixed with molten copper smelting slag and then subjected to heat treatment to obtain a vitrified melt; the temperature of the molten copper smelting slag is 1300℃.

[0072] Molten copper smelting slag: originating from the side-blown smelting furnace slag of a large copper smelter in Yunnan; see also Figure 2 As shown, the main phases in the smelting slag are iron(III) oxide and ferrous silicate. The elemental composition of the molten copper smelting slag by mass fraction includes: Si 14.77%, Fe 42%, Ca 2.073%, Al 3.318%, Zn 1.716%, and O 30.14%.

[0073] S21. The pretreated clinker is transferred to a storage silo above the high-temperature furnace via a closed conveyor belt. By controlling the discharge valve of the storage silo, the material flows at a constant rate into a pre-arranged slag bale via a high-temperature resistant chute (inclination angle controlled at 35°). The slag bale is a steel-shell refractory-lined structure with a volume of 10 m³. 3 The actual filling volume is controlled at around 85% of its volume.

[0074] S22. The high-temperature molten copper slag at 1300℃ in the side-blown melting furnace is continuously and steadily discharged into the slag bag containing the pre-treated clinker through the slag outlet and refractory chute (inclination angle 30°). The high temperature of the molten copper slag causes the arsenic-containing materials and additives to undergo a melting reaction. The melting temperature is controlled within the range of 1250-1350℃, and the holding time is not less than 30 minutes to ensure sufficient formation of the glass phase and obtain a glassy melt.

[0075] S3. The vitrified melt is cooled to obtain an arsenic-containing glass solidified body.

[0076] The slag bag containing the vitrified molten material is transported to a dedicated slow cooling area and naturally air-cooled for 34 hours under ambient atmospheric conditions to allow the molten material to initially solidify and release thermal stress. After air cooling, it undergoes forced water cooling for 72 hours, with uniform spraying of cooling water to rapidly cool the slag body, forming a stable glassy structure, thus obtaining an arsenic-containing glassy solidified body.

[0077] Experimental results: After cooling, samples of the vitrified solidified body are taken for analysis. For example... Figure 3 XRD analysis showed no arsenic-containing phases; the arsenic was solidified within the vitreous body as an amorphous phase. Arsenic leaching toxicity testing was conducted according to the "Identification Standard for Hazardous Waste - Leaching Toxicity Identification" (GB5085.3-2007), and the results showed an arsenic leaching concentration of 0.61 mg / L, far below the national standard limit (5 mg / L). Figure 4 The solidified body shown has good physical integrity and a dense glassy surface layer.

[0078] Comparative Example 1 Compared to Example 1, the other conditions in this comparative example remain unchanged, except for the pretreatment step in step S1: instead of granulating the arsenic-containing material, the arsenic-containing material, calcium-silicon additive, and modifier are directly mixed evenly in a closed mixer in proportion, and the mixing time is not less than 30 minutes to ensure uniform material distribution and obtain pretreated clinker.

[0079] Experimental results: After cooling, the vitrified solidified body was sampled and analyzed. Arsenic leaching toxicity was tested according to the "Identification Standard for Hazardous Waste - Leaching Toxicity Identification" (GB 5085.3-2007). The results showed that the arsenic leaching concentration was 2.33 mg / L.

[0080] Comparative Example 2 Compared to Example 1, all other conditions in this comparative example remained unchanged, except that the mass ratio of arsenic-containing material, calcium-silicon additive, and modified agent in the arsenic-containing mixture was adjusted to 1:0.25:0.3, that is, only the amount of calcium-silicon additive added was adjusted.

[0081] Experimental results: After cooling, the vitrified solidified body was sampled and analyzed. Arsenic leaching toxicity was tested according to the "Identification Standard for Hazardous Waste - Leaching Toxicity Identification" (GB 5085.3-2007), and the results showed that the arsenic leaching concentration was 1.82 mg / L.

[0082] Comparative Example 3 Compared to Example 1, all other conditions in this comparative example remain unchanged, except that the temperature of the molten copper slag is adjusted to 1100°C.

[0083] Experimental results: After cooling, samples of the vitrified solidified body were taken for analysis. Arsenic leaching toxicity was tested according to the "Identification Standard for Hazardous Waste - Leaching Toxicity Identification" (GB 5085.3-2007), and the results showed that the arsenic leaching concentration was 3.4 mg / L.

[0084] Comparative Example 4 Compared to Example 1, the conditions in this comparative example remain unchanged except that the duration of natural air cooling in step S3 is adjusted to 58 hours.

[0085] Experimental results: After cooling, the vitrified solidified body was sampled and analyzed. Arsenic leaching toxicity was tested according to the "Identification Standard for Hazardous Waste - Leaching Toxicity Identification" (GB 5085.3-2007). The results showed that the arsenic leaching concentration was 2.65 mg / L.

[0086] Furthermore, the actual image of the arsenic-containing glass curing product prepared in this comparative example is shown below. Figure 5 As shown, with Figure 4 Compared with the arsenic-containing glass cured product prepared in Example 1, the surface gloss of the edge portion weakens as the cooling time increases, and the degree of vitrification of this comparative product is significantly weaker than that of the product in Example 1.

[0087] The above technical solutions of the present invention are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made under the technical concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included in the patent protection scope of the present invention.

Claims

1. A method for solidifying arsenic-containing materials and co-processing copper smelting slag, characterized in that, Including the following steps: Pre-treatment of an arsenic-containing mixture yields pre-treated clinker; the arsenic-containing mixture includes arsenic-containing materials, calcium-silicon additives, and modifiers. The pretreated clinker is mixed with molten copper smelting slag and then subjected to heat treatment to obtain a vitrified melt; the temperature of the molten copper smelting slag is 1250-1350℃. The vitrified melt is cooled to obtain an arsenic-containing glass solidified body.

2. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The composition of the arsenic-containing mixture includes arsenic-containing materials, calcium-silicon additives, and modifiers in a mass ratio of 0.5-1:0.3-0.6:0.2-0.

4.

3. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The amount of arsenic-containing material added is 0.5-1t / 20t of smelting slag; the amount of calcium-silicon additive added is 0.3-0.6t / 20t of smelting slag; and the amount of the modifier added is 5-20kg / t of smelting slag.

4. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The calcium-silicon additive comprises calcium oxide and silicon oxide, and the calcium-silicon ratio of the calcium-silicon additive is 1:2.5-5. The modified agent includes anhydrous sodium borate.

5. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The pretreatment includes: granulating the arsenic-containing material to obtain an arsenic-containing precursor; and mixing the arsenic-containing precursor with the calcium-silicon additive and the modifier to obtain the pretreated clinker.

6. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The composition of the arsenic-containing material, by mass fraction, includes, but is not limited to: As 10-20%, Cu 8-15%, Pb 15-22%, S 0-8%, Si 0-2%, Fe 0-8%, with the remainder being oxygen and other unavoidable impurity elements.

7. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The main phases in the molten copper smelting slag include iron(II,III) oxide and / or ferrous silicate; by mass fraction, the elemental composition of the molten copper smelting slag includes: Si 10-20%, Fe 40-50%, Ca 1-5%, Al 1-5%, Zn 0.5-3%, O 20-50%, with the remainder being unavoidable impurity elements.

8. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The temperature of the heat preservation treatment is 1250-1350℃, and the duration of the heat preservation treatment is 30-60 minutes; The cooling process includes air cooling and water cooling, wherein the air cooling duration is 24-48 hours and the water cooling duration is 48-72 hours.

9. The method for solidifying arsenic-containing materials and co-processing copper smelting slag according to claim 1, characterized in that, The arsenic leaching concentration of the arsenic-containing glass curing body is less than 0.5 mg / L; the arsenic element in the arsenic-containing glass curing body exists in the form of an amorphous glass phase.

10. The application of the method for solidifying arsenic-containing materials and co-processing copper smelting slag as described in any one of claims 1-9 in the treatment of arsenic-containing materials.

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