High-performance beryllium slag glass solidified body and preparation method thereof

Abstract

The invention discloses a high-performance beryllium slag glass solidified body and a preparation method thereof, and belongs to the field of green disposal and recycling of solid wastes. Firstly, beryllium slag and solid waste auxiliary materials are dried and evenly mixed with reducing coal according to a certain proportion, and a mixed raw material is obtained; then, heating the mixed raw materials according to a certain heating system to obtain a melt; smoke generated in the melting process of the mixed raw materials is discharged after being subjected to dedusting and tail gas treatment and reaching the standard, and dedusting ash can be returned to the mixing process to be used as an ingredient. And finally, carrying out water quenching on the melt to obtain a beryllium slag glass solidified body and an alloy. The method has the advantages of being large in beryllium slag absorption amount, good in beryllium solidification effect, high in resource utilization rate, low in production cost and the like. The prepared beryllium slag glass solidified body has the excellent performance that the Be leaching concentration is smaller than 0.002 mg / L, the glass phase content is larger than 85%, the acid dissolution loss rate is smaller than 3%, the compressive strength is larger than or equal to 100 MPa, the crushing value is smaller than or equal to 23%, the firmness is smaller than or equal to 4%, and the beryllium slag glass solidified body can be widely applied to the fields of concrete, cement, filling, pavements, wall heat preservation and the like.

Description

Technical Field

[0001] The present invention belongs to the field of comprehensive utilization of solid waste, and particularly relates to a method for preparing a high-strength beryllium slag glass solidified body from beryllium slag and a preparation method thereof. Background Art

[0002] Beryllium and its compounds have characteristics such as high specific elastic modulus stiffness, high specific strength, good thermal conductivity, dimensional stability, and strong heat conduction ability, and have important uses in the fields of national defense and military industry, atomic energy, aerospace and aviation, scientific instruments and meters, metallurgy, etc.

[0003] Beryllium ore and calcite are subjected to processes such as smelting, acid leaching, evaporation crystallization, iron removal by neutralization, precipitation, and calcination to obtain beryllium hydroxide and industrial beryllium oxide. A large amount of beryllium-containing slag, dust collected by a dust collection device (removal device), and wastewater treatment sludge are generated during the production process of beryllium and its compounds. Beryllium is a highly toxic element. Inhaling high concentrations of beryllium and its compounds in the short term can cause acute berylliosis; long-term exposure to low concentrations of beryllium and its compounds can cause chronic berylliosis. The green disposal and resource utilization of beryllium slag have become major problems that need to be solved urgently in the beryllium smelting industry. Chinese Patent CN 116282978A discloses a method for resource disposal and application of beryllium-containing silicon slag: mixing the beryllium-containing silicon slag with auxiliary materials evenly and roasting at 850°C to 1300°C to obtain a roasted sample. The auxiliary material is a kind of coal for reduction, with a fixed carbon content greater than 55% and a calorific value greater than 4000 kcal / kg. The addition amount of the auxiliary material is 4% to 12% of the mass of the beryllium-containing silicon slag. The disposal process of the present invention is simple, with less equipment investment, low operating cost, good solidification effect of the roasted product, no secondary pollution, meeting the requirements of safe, efficient, and green disposal of beryllium-containing silicon slag. The obtained roasted sample of beryllium-containing silicon slag can be used to prepare a cement clinker admixture, enabling the resource disposal of beryllium-containing silicon slag. However, this technology can achieve the solidification of beryllium, but is limited to beryllium-containing silicon slag, with a narrow application range.

[0004] Chinese Patent CN 109706327A discloses a method for harmless disposal of beryllium slag: using beryllium slag as an auxiliary material for slag blending in blast furnace lead smelting, crushing and mixing it with the raw materials for traditional blast furnace lead smelting, pressing it into shaped furnace charge, and then putting it into the blast furnace for smelting according to the traditional lead smelting method. The soluble beryllium sulfate in the beryllium slag thermally decomposes and oxidizes into beryllium oxide during the smelting process, and is dispersed in the slag-forming components silicon, iron, and calcium of the furnace charge. After melting by slag formation, the beryllium oxide is coated by the silicon-iron-calcium slag, so as to reduce the amount of soluble beryllium sulfate in the beryllium slag and prevent it from being dissolved out in an acid rain environment. The present invention can utilize the equipment and mature technology of existing lead smelting enterprises for large-scale harmless disposal, saving a large amount of investment in environmental protection special funds, with high economic and environmental benefits; the disposed slag achieves "reduction in quantity" and "harmlessness", and can be reused. However, the beryllium slag blending ratio of this technology is low, and the quality of the crude lead alloy is easily affected.

[0005] Chinese Patent CN 109761514A discloses a system and process for detoxifying beryllium slag and co - processing it with a cement kiln for resource utilization: when beryllium slag is washed with water under acidic conditions, a beryllium sulfate solution and solid slag can be formed. After the beryllium sulfate solution reacts with ammonia water, beryllium hydroxide precipitation is generated. After the precipitation is separated, it is used to recover beryllium hydroxide; while the solid slag is sent to the cement kiln of the system for high - temperature calcination after treatment, and the beryllium contained in the solid slag is fixed in the lattice of cement clinker to form minerals such as calcium ferro - beryllate, calcium alumino - beryllate, and calcium beryllate. The beryllium content in the cement reaches trace amounts, and the leaching solubility is less than 0.1 μg / L, meeting the requirements of cement raw materials. The ammonia - nitrogen compounds generated during the reaction are converted into ammonia water or ammonium salts, which can be used as a denitrification agent for the cement kiln or returned to the beryllium smelting plant as an auxiliary agent. However, this technology has a complex process flow, high operating costs, and a high risk of beryllium leaching when used as cement clinker.

[0006] Chinese Patent CN 109453493A discloses a stabilizing agent for treating beryllium - containing waste residue, its preparation method and application: The stabilizing agent for treating beryllium - containing waste residue of the present invention includes the following components by mass fraction: 15 - 25 parts of a conditioner, 5 - 15 parts of an additive, and 60 - 80 parts of a curing agent. The conditioner is fly ash, sepiolite, or sludge from a water treatment plant, and the additive is potassium dihydrogen phosphate, superphosphate, sodium sulfide, or calcium oxide. The stabilizing agent for treating beryllium - containing waste residue of the present invention can significantly stabilize and solidify beryllium and fluorine in the beryllium - containing waste residue, greatly reducing the leaching concentration of beryllium and fluorine in the beryllium - containing waste residue. The solidification rate reaches more than 99%, and the leaching concentration of beryllium is lower than the leaching toxicity identification standard value, realizing the transformation of the beryllium - containing waste residue from hazardous waste to general solid waste; this stabilizing agent has low cost, simple preparation method and use method, and is conducive to popularization and application. However, this technology has a complex process flow, and the storage volume of the beryllium - containing waste residue increases after treatment.

[0007] Beryllium slag contains a large amount of volatile substances, and beryllium exists in unstable forms such as sulfates. This makes the treatment of beryllium slag not only consider the performance of the final product, but also pay attention to the solidification effect of beryllium and avoid pollution. Different from the above - mentioned methods, glass has a dense glass network that can encapsulate beryllium in the glass matrix to achieve the solidification of beryllium, with good chemical stability, strong anti - leaching ability, and excellent durability. Therefore, it is urgent to study a preparation method of a glass solidification body based on beryllium slag to effectively solve the problems of beryllium solidification and environmental pollution control. Summary of the Invention

[0008] Aiming at the technical problems existing in the existing beryllium slag resource disposal technologies, such as poor beryllium solidification effect, low beryllium slag consumption, single type of beryllium slag disposal, and the increase in volume and quantity of beryllium slag after disposal, the present invention discloses a high - performance beryllium slag glass solidification body and its preparation method. The beryllium slag glass solidification body prepared by the present invention has the advantages of large beryllium slag consumption, good beryllium solidification effect, high resource utilization rate, and low production cost.

[0009] The present invention is achieved through the following technical solutions:

[0010] A high-performance beryllium slag glass solidified body, characterized in that the dried beryllium slag, solid waste auxiliary materials and reducing coal are mixed evenly in a certain proportion and then melted and water-quenched to obtain the beryllium slag glass solidified body; by adjusting the ratio of beryllium slag to solid waste auxiliary materials, the contents of SiO2, Al2O3, and CaO in the mixed raw materials are adjusted to improve the glass phase yield; the performance of the prepared beryllium slag glass solidified body: Be leaching concentration < 0.002 mg / L, glass phase content > 85%, acid dissolution loss rate < 3%, compressive strength ≥ 100 MPa, crushing value ≤ 23%, soundness ≤ 4%.

[0011] A preparation method of a high-performance beryllium slag glass solidified body as described above, characterized by including the following steps:

[0012] (1) Establish a ternary melting system model of beryllium slag CaO-SiO2-Al2O3, draw the phase diagram of the CaO-SiO2-Al2O3 ternary melting system, and determine the dominant region for the formation of the molten liquid phase; among them, the component ratios in the dominant region are: CaO 15% - 30%, Al2O3 5% - 25%, SiO2 45% - 65%;

[0013] (2) Detect the component contents of CaO, SiO2, and Al2O3 in the beryllium slag, and normalize the CaO, SiO2, and Al2O3 three phases of the beryllium slag so that their sum is 1 (component ratio normalization is a method of converting data into percentage form, commonly used in the data processing stage. Since the composition of beryllium slag is relatively complex, but the main components are calcium, aluminum, and silicon, normalizing the three makes it easier to directly understand the relative importance of each component), mark and analyze the phase transformation, solidus line, liquidus line, etc. of beryllium slag with different compositions in the phase diagram;

[0014] (3) Judge whether the beryllium slag data is within the dominant region determined in step (1). If the beryllium slag data is within the dominant region, proceed to step (6); if the beryllium slag data is outside the dominant region, proceed to step (4);

[0015] (4) Drying: Dry the beryllium slag and solid waste auxiliary materials;

[0016] (5) Mixing: Mix the dried beryllium slag, solid waste auxiliary materials and reducing coal evenly in a certain proportion to obtain a mixed raw material;

[0017] (6) Melting: Heat the beryllium slag described in step (3) or the mixed raw material obtained in step (5) to melt in two steps to obtain a melt. The flue gas generated during the heating process is discharged after passing through dust removal and tail gas treatment to meet the standards, and the dust removal ash can be returned to the mixing process for use as a batching material;

[0018] (7) Water quenching: Water quench the melt obtained in step (6) to obtain a beryllium slag glass solidified body and an alloy.

[0019] Further, the beryllium slag described in step (1) is composed of one or more of the slag generated during the production of beryllium and its compounds, the dust collected by the dust collection (removal) device, and the wastewater treatment sludge. The Be leaching concentration is 20 - 35 mg / L, and the SO3 content is 10% - 70%.

[0020] Further, the solid waste auxiliary material described in step (2) is a solid waste or a solid waste mixture containing calcium, aluminum, and silicon. The CaO content is 1% - 90%, the Al2O3 content is 0.5% - 80%, and the SiO2 content is 2% - 65%. The fixed carbon content in the reduction coal is greater than 60%, the calorific value is greater than 4500 kcal / kg, and the sulfur content is less than 1%. The dosage of the added reduction coal accounts for 10 - 25% of the mass of the mixed raw materials.

[0021] Further, the mixed raw materials described in step (6) are first heated to 800°C - 1100°C and kept warm for 0.5 - 3 h; then, heated to 1300°C - 1500°C and kept warm for 0.5 - 3 h.

[0022] The technical key points of the present invention are as follows:

[0023] 1. The main components of the beryllium slag are calcium, aluminum, silicon, and sulfur, which provide the necessary components for glass formation. At the same time, SO3 in the beryllium slag volatilizes as the melting temperature rises. Therefore, assuming that the beryllium slag is completely composed of the three phases of CaO - Al2O3 - SiO2, based on the CaO - Al2O3 - SiO2 ternary phase diagram, by normalizing the calcium, aluminum, and silicon contents of the beryllium slag so that their sum is 1, the phase changes, solidus, liquidus, etc. of different components are marked and analyzed in the phase diagram to explore the conditions for preparing the beryllium slag glass solidified body. Through software simulation and a large number of experiments by the applicant, it is determined that when the mixing ratio of the glass - forming components such as CaO, Al2O3, and SiO2 in the mixed raw materials is within the dominant region of CaO 15% - 30%, Al2O3 5% - 25%, and SiO2 45% - 65%, the glass phase yield is high, so that beryllium is solidified in the glass network. The applicant found that beryllium is mainly solidified in the glass network, but due to the differences in the types of beryllium slag, the calcium, aluminum, and silicon component contents in the beryllium slag are not sufficient to generate enough glass phase to achieve the purpose of solidifying beryllium. The method adopted in the present invention is:

[0024] Using solid wastes or solid waste mixtures containing calcium, aluminum, and silicon such as secondary aluminum ash slag, desulfurized gypsum, waste glass, and carbide slag to complement the components with beryllium slag, so that the mixing ratio of the mixed raw materials is within the dominant region, thereby increasing the glass phase yield and forming a Ca - Al - Si glass solidified body with good stability, so that the toxic element beryllium is completely solidified in the glass network.

[0025] 2. The beryllium slag and auxiliary materials contain some heavy metals such as iron and copper. During the melting process, the crystallization phase induced by heavy metals has an adverse effect on the properties of the glass solidified body. In the present invention, by adding reducing coal, valuable metals such as copper, iron, and tin in the mixed raw materials are reduced, and a crude alloy is recovered. The remaining reducing coal can provide an additional heat source for the reaction and improve the melting efficiency. If the addition amount of reducing coal is less than 10%, the reaction will be incomplete and there will still be some heavy metals remaining; if the addition amount is greater than 20%, there will be too much residual auxiliary materials.

[0026] CuO + CO → Cu + CO2

[0027] Cu2O + CO → 2Cu + CO2

[0028] FeO + CO → Fe + CO2

[0029] Fe2O3 + 3CO → 2Fe + 3CO2

[0030] SnO + CO → Sn + CO2

[0031] SnO2 + 2CO → Sn + 2CO2

[0032] 3. The beryllium slag contains a large amount of sulfate components. When heated to the required temperature in one step, a large amount of sulfur dioxide gas is generated, resulting in structural defects and crystallization or delamination phenomena in the glass solidified body. The method adopted in the present invention is two-stage heating.

[0033] ① The first heating stage (800°C - 1100°C, holding for 0.5 - 3 h): The reducing coal decomposes to form a reducing atmosphere, and the metal oxides are reduced. The crude metal can be recovered during the water quenching process; the sulfur volatilization rate is reduced, the pore defects of the glass solidified body are reduced, and the structure of the solidified body is more dense and stable; the components are initially uniformly mixed and reacted, maintaining the uniformity of the melt, and avoiding crystallization or delamination phenomena caused by overheating or undercooling due to uneven composition at high temperatures.

[0034] ② The second heating stage (1300°C - 1500°C, holding for 0.5 - 3 h): The raw materials are completely melted, the viscosity of the melt is reduced, and the fluidity is improved, so that the bubbles quickly overflow from the melt; the residual sulfur, chlorine and other volatile substances in the melt are completely removed, reducing the retention of gas in the melt.

[0035] The beneficial technical effects of the present invention:

[0036] (1) In the method of the present invention, the composition of the beryllium slag glass solidified body is regulated by using solid waste or solid waste mixture auxiliary materials. On the one hand, the consumption amount of beryllium slag can be greatly increased; on the other hand, the production cost is reduced. It not only realizes the solidification of the toxic element beryllium, but also realizes the harmlessness and resource utilization of solid waste.

[0037] (2) In the method of the present invention, reducing coal is additionally added and heated in two stages. On the one hand, the melting energy consumption is reduced, the metal recovery rate is increased, and resource waste is avoided. On the other hand, the sulfates in the raw materials are completely decomposed, the gas release process is more stable, the retention of sulfur gas in the glass melt is reduced, and the performance degradation of the beryllium slag glass solidified body caused by uneven crystallization is prevented.

[0038] (3) The beryllium slag glass solidified body prepared by the method of the present invention has the characteristics of being green and having high strength. The Be leaching concentration and mechanical properties of the prepared beryllium slag glass solidified body are as follows: Be leaching concentration < 0.002 mg / L, glass phase content > 85%, acid dissolution loss rate < 3%, compressive strength ≥ 100 MPa, crushing value ≤ 23%, soundness ≤ 4%. The beryllium leaching concentration is lower than the safety limit of "Technical Requirements for Products of Vitrification Treatment of Solid Wastes" (GB / T 41015-2021), and it can be used in fields such as concrete, cement, filling, road surface, and wall thermal insulation materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a process flow chart of the method of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0040] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0041] On the contrary, the present invention covers any alternatives, modifications, equivalent methods and solutions made within the essence and scope of the present invention defined by the claims. Further, in order to enable the public to better understand the present invention, some specific details are described in detail in the following detailed description of the present invention. Those skilled in the art can fully understand the present invention without the description of these details.

[0042] Example 1

[0043] The beryllium slag in this example is the beryllium slag generated during the production of beryllium oxide. Its main chemical composition is SiO2 54.39%, Al2O3 5.61%, CaO 19.68%, SO3 14.18%, and the balance is iron oxide, magnesium oxide, sodium oxide, etc. The beryllium leaching concentration is 30.6 mg / L. The calcium, aluminum, and silicon in the beryllium slag are normalized to obtain the component data of the beryllium slag as SiO2 68.26%, Al2O3 7.04%, and CaO 24.7%. The data of the beryllium slag in this example is outside the advantageous region, and an additional aluminum source needs to be supplemented. The auxiliary material is secondary aluminum ash slag, in which SiO2 is 4.6%, Al2O3 is 62.8%, and CaO is 1.5%. The fixed carbon content in the reducing coal is 62.31%, the S content is 0.88%, and the calorific value is 4550 kcal / kg.

[0044] Dry the beryllium slag and the solid waste auxiliary material, take 100 parts of beryllium slag, 30 parts of secondary aluminum ash slag, and 15% of reducing coal and mix them evenly. The contents of silicon, aluminum, and calcium in the adjusted mixed raw material are: SiO2 53.57%, Al2O3 19.91, and CaO 19.35%.

[0045] First, heat the mixed raw material to 1050 °C and hold for 0.5 h. Then, heat it to 1370 °C and hold for 3 h. After the holding is completed, perform water quenching treatment to obtain a glass solidified body and crude metal. The flue gas generated during the melting process enters the flue gas treatment facility and is discharged after meeting the pollutant discharge standards. Take a certain amount of water quenched slag for testing to obtain the beryllium leaching concentration, glass phase content, and mechanical indexes: the Be leaching concentration is 0.00039 mg / L, the glass phase content is 94.7%, the acid dissolution loss rate is 0.18%, the compressive strength is 434.73 MPa, the crushing value is 22%, and the soundness is 3%.

[0046] Example 2

[0047] The beryllium slag in this example is the wastewater treatment sludge generated during the production of beryllium oxide. Analyze its composition. The main chemical composition is SiO2 57.62%, Al2O3 13.26, CaO 5.61%, SO3 10.21%, and the balance is iron oxide, magnesium oxide, sodium oxide, etc. The beryllium leaching concentration is 31.03 mg / L. The calcium, aluminum, and silicon in the beryllium slag are normalized to obtain the component data of the beryllium slag as SiO2 73.41%, Al2O3 16.89%, and CaO 9.7%. The data of the beryllium slag in this example is outside the advantageous region. An additional calcium source needs to be supplemented. The auxiliary material is carbide slag, in which SiO2 is 3.12%, Al2O3 is 1.14%, and CaO is 62.12%. The fixed carbon content in the reducing coal is 65.34%, the S content is 0.82%, and the calorific value is 6896 kcal / kg.

[0048] Dry the beryllium slag and solid waste auxiliary materials. Take 100 parts of beryllium slag, 60 parts of carbide slag, and 18% of reduction coal and mix them evenly. The contents of silicon, aluminum, and calcium in the adjusted mixed raw materials are: SiO2 47.05%, Al2O3 10.98%, CaO 29.35%.

[0049] First, heat the mixed raw materials to 970°C and hold for 2.7 h. Then, heat to 1420°C and hold for 1.3 h. After the holding ends, carry out water quenching treatment to obtain a glass solidified body and crude metal; the flue gas generated during the melting process enters the flue gas treatment facility and is discharged after meeting the pollutant emission standards. Take a certain amount of water quenched slag for testing to obtain the beryllium leaching concentration, glass phase content, and mechanical indexes: Be leaching concentration is 0.00076 mg / L, glass phase content is 94.26%, acid dissolution loss rate is 0.21%, compressive strength is 186.21 MPa, crushing value is 22.3%, and soundness is 2.9%.

[0050] Example 3

[0051] The beryllium slag in this example is the beryllium slag generated during the production of beryllium oxide. Analyze its components. The main chemical composition is SiO2 33.26%, Al2O3 3.82%, CaO 16.27%, SO3 37.78%, and the balance is iron oxide, magnesium oxide, sodium oxide, etc. The beryllium leaching concentration is 31.92 mg / L. Normalize the calcium, aluminum, and silicon in the beryllium slag to obtain the component data of the beryllium slag as SiO2 62.34%, Al2O3 5.23%, CaO 25.94%; the data of the beryllium slag in this example is outside the dominant region, and an additional aluminum source needs to be supplemented. The auxiliary material is secondary aluminum ash slag, in which SiO2 is 5.6%, Al2O3 is 72.62%, and CaO is 1.79%. The fixed carbon content in the reduction coal is 64.35%, the S content is 0.91%, and the calorific value is 4680 kcal / kg.

[0052] Dry the beryllium slag and solid waste auxiliary materials. Take 100 parts of beryllium slag, 26 parts of secondary aluminum ash slag, and 14% of reduction coal and mix them evenly. The contents of silicon, aluminum, and calcium in the adjusted mixed raw materials are: SiO2 50.63%, Al2O3 19.14%, CaO 20.96%.

[0053] First, heat the mixed raw materials to 820 °C and hold for 3 h. Then, heat to 1300 °C and hold for 1.8 h. After the holding is completed, perform water quenching treatment to obtain a glass solidified body and crude metal; the flue gas generated during the melting process enters the flue gas treatment facility and is discharged after meeting the pollutant discharge standards. Take a certain amount of water quenched slag for testing to obtain the beryllium leaching concentration, glass phase content and mechanical indexes: the Be leaching concentration is 0.00135 mg / L, the glass phase content is 94.6%, the acid dissolution loss rate is 0.7%, the compressive strength is 171 MPa, the crushing value is 22.9%, and the soundness is 2.8%.

[0054] Example 4

[0055] The beryllium slag in this example is the beryllium slag generated during the production of metallic beryllium. Analyze its composition. The main chemical components are SiO2 40.37%, Al2O3 5.26%, CaO 13.78%, SO3 31.37%, and the balance is iron oxide, magnesium oxide, sodium oxide, etc. The beryllium leaching concentration is 32.7 mg / L. Normalize the calcium, aluminum and silicon in the beryllium slag to obtain the component data of the beryllium slag as SiO2 67.95%, Al2O3 8.85%, CaO 23.19%; the data of the beryllium slag in this example is outside the dominant area, and an additional calcium source needs to be supplemented. The auxiliary material is desulfurized gypsum, in which SiO2 is 3.12%, Al2O3 is 0.93%, and CaO is 43.27%; secondary aluminum ash slag, in which SiO2 is 4.93%, Al2O3 is 76.86%, and CaO is 1.26%. The fixed carbon content in the reducing coal is 68.76%, the S content is 0.82%, and the calorific value is 4820 kcal / kg.

[0056] Dry the beryllium slag and solid waste auxiliary materials. Take 100 parts of beryllium slag, 20 parts of desulfurized gypsum, 10 parts of secondary aluminum ash slag, and 20% of reducing coal; the contents of silicon, aluminum and calcium in the adjusted mixed raw materials are: SiO2 53.13%, Al2O3 12.86%, CaO 24.59%.

[0057] First, heat the mixed raw materials to 1100 °C and hold for 3 h. Then, heat to 1500 °C and hold for 0.5 h. After the holding is completed, perform water quenching treatment to obtain a glass solidified body and crude metal; the flue gas generated during the melting process enters the flue gas treatment facility and is discharged after meeting the pollutant discharge standards. Take a certain amount of water quenched slag for testing to obtain the beryllium leaching concentration, glass phase content and mechanical indexes: the Be leaching concentration is 0.00062 mg / L, the glass phase content is 89.03%, the acid dissolution loss rate is 0.12%, the compressive strength is 306.05 MPa, the crushing value is 23.1%, and the soundness is 3.5%.

[0058] Example 5

[0059] The beryllium slag in this example is the beryllium slag generated during the production of metallic beryllium. Its composition is analyzed, and the main chemical components are SiO2 0.56%, Al2O3 21.81%, CaO 1.13%, SO3 66.81%, and the balance is iron oxide, magnesium oxide, sodium oxide, etc. The beryllium leaching concentration is 29.86 mg / L. The calcium, aluminum, and silicon phases of the beryllium slag are normalized, and the component data of the beryllium slag are obtained as SiO2 2.38%, Al2O3 92.81%, and CaO 4.81%. The data of the beryllium slag in this example is outside the dominant region, and additional silicon source and calcium source need to be supplemented. The auxiliary material is waste glass, in which SiO2 is 60.2%, Al2O3 is 11.68%, and CaO is 22.62%. The fixed carbon content in the reducing coal is 68.76%, the S content is 0.82%, and the calorific value is 4969 kcal / kg.

[0060] The beryllium slag and the solid waste auxiliary material are dried. Take 10 parts of beryllium slag, 90 parts of waste glass, and 10% of reducing coal. The contents of silicon, aluminum, and calcium in the adjusted mixed raw material are: SiO2 49.22%, Al2O3 19.79%, and CaO 20.84%.

[0061] The mixed raw material is first heated to 1100 °C and held for 2 h. Then, it is heated to 1500 °C and held for 2.5 h. After the holding is completed, water quenching treatment is used to obtain a glass solidified body and crude metal. The flue gas generated during the melting process enters the flue gas treatment facility and is discharged after meeting the pollutant discharge standards. A quantitative amount of water quenched slag is taken for testing to obtain the beryllium leaching concentration, glass phase content, and mechanical indexes: the Be leaching concentration is 0.00096 mg / L, the glass phase content is 94.88%, the acid dissolution loss rate is 0.66%, the compressive strength is 111.15 MPa, the crushing value is 21.4%, and the soundness is 3.2%.

[0062] Example 6

[0063] The beryllium slag in this embodiment is the dust collected in the dust removal device during the production of beryllium oxide. Its composition is analyzed, and the main chemical components are SiO2 45.84%, Al2O3 18.06%, CaO 10.14%, SO3 14.61%, and the balance is iron oxide, magnesium oxide, sodium oxide, etc. The beryllium leaching concentration is 21.06 mg / L. The calcium, aluminum, and silicon in the beryllium slag are normalized, and the component data of the beryllium slag are obtained as SiO2 61.91%, Al2O3 24.39%, and CaO 13.7%; the data of the beryllium slag in this embodiment is outside the dominant region, and an additional calcium source needs to be supplemented. The auxiliary material is desulfurized gypsum, in which SiO2 is 2.29%, Al2O3 is 0.94%, and CaO is 48.16%; the fixed carbon content in the reducing coal is 68.34%, the S content is 0.83%, and the calorific value is 6910 kcal / kg.

[0064] Dry the beryllium slag and solid waste auxiliary materials, take 100 parts of beryllium slag, 30 parts of desulfurized gypsum, and 18% of reducing coal; the contents of silicon, aluminum, and calcium in the adjusted mixed raw materials are: SiO2 48.15%, Al2O3 18.98%, and CaO 21.65%.

[0065] First, heat the mixed raw materials to 1000 °C and keep them warm for 2.5 h. Then, heat them to 1350 °C and keep them warm for 1.5 h. After the heat preservation is completed, water quenching treatment is used to obtain a glass solidified body and crude metal; the flue gas generated during the melting process enters the flue gas treatment facility and is discharged after meeting the pollutant emission standards. Take a certain amount of water quenched slag for testing to obtain the beryllium leaching concentration, glass phase content, and mechanical indexes: the Be leaching concentration is 0.00026 mg / L, the glass phase content is 93.65%, the acid dissolution loss rate is 0.26%, the compressive strength is 311.41 MPa, the crushing value is 23.83%, and the soundness is 2.8%.

Claims

1. A high-performance beryllium slag vitrified body, characterized in that, The dried beryllium slag, solid waste auxiliary materials and reducing coal are mixed evenly in a certain proportion, melted and then water-quenched to obtain a beryllium slag glass solidified body; by adjusting the ratio of beryllium slag to solid waste auxiliary materials, the contents of SiO2, Al2O3 and CaO in the mixed raw materials are adjusted to improve the glass phase yield; the performance of the prepared beryllium slag glass solidified body: Be leaching concentration < 0.002mg / L, glass phase content > 85%, acid dissolution loss rate < 3%, compressive strength ≥ 100MPa, crushing value ≤ 23%, soundness ≤ 4%.

2. The preparation method of the high-performance beryllium slag glass solidified body according to claim 1, characterized in that, It includes the following steps: (1) Establish a ternary melting system model of beryllium slag CaO-SiO2-Al2O3, draw the phase diagram of the ternary melting system of CaO-SiO2-Al2O3, and determine the dominant region for the formation of molten liquid phase; among them, the component ratios in the dominant region are: CaO 15%-30%, Al2O3 5%-25%, SiO2 45%-65%; (2) Detect the component contents of CaO, SiO2 and Al2O3 in the beryllium slag, and normalize the CaO, SiO2 and Al2O3 three phases of the beryllium slag so that their sum is 1, and mark and analyze the phase change, solidus line and liquidus line of beryllium slag with different components in the phase diagram; (3) Judge whether the beryllium slag data is within the dominant region determined in step (1). If the beryllium slag data is within the dominant region, step (6) is carried out. If the beryllium slag data is outside the dominant region, step (4) is carried out; (4) Drying: Dry the beryllium slag and solid waste auxiliary materials; (5) Mixing: Mix the dried beryllium slag, solid waste auxiliary materials and reducing coal evenly in a certain proportion to obtain a mixed raw material; (6) Melting: The beryllium slag described in step (3) or the mixed raw material obtained in step (5) is heated for melting in two steps to obtain a melt. The flue gas generated during the heating process is discharged after dust removal and tail gas treatment up to the standard. The dust removed can be returned to the mixing process as batching; (7) Water quenching: Quench the melt obtained in step (6) with water to obtain a beryllium slag glass solidified body and an alloy.

3. The preparation method of a high-performance beryllium slag glass solidified body according to claim 2, characterized in that, The beryllium slag described in step (1) is composed of one or several of the molten slag generated during the production of beryllium and its compounds, the dust collected by the dust collection (removal) device and the wastewater treatment sludge. The Be leaching concentration is 20-35mg / L, and the SO3 content is 10%-70%.

4. The preparation method of a high-performance beryllium slag vitrified body according to claim 2, characterized in that, The solid waste auxiliary materials described in step (2) are solid wastes or solid waste mixtures containing calcium, aluminum and silicon. The CaO content is 1%-90%, the Al2O3 content is 0.5%-80%, and the SiO2 content is 2%-65%; the fixed carbon content in the reducing coal is greater than 60%, the calorific value is greater than 4500kcal / kg, and the sulfur content is less than 1%; the dosage of the added reducing coal accounts for 10-20% of the mass of the mixed raw material.

5. The preparation method of a high-performance beryllium slag glass solidified body according to claim 2, characterized in that, The mixed raw material described in step (6) is first heated to 800°C - 1100°C and kept warm for 0.5 - 3h; then, it is heated to 1300°C - 1500°C and kept warm for 0.5 - 3h.

Images