Decorative glass based on metallurgical slag and process for its preparation

Abstract

This invention relates to the field of colored glass preparation, specifically to a decorative glass based on metallurgical waste slag and its preparation process. The key technical points are as follows: the raw materials for preparing the decorative glass include nickel-iron slag and ferrosilicon slag; wherein the mass ratio of nickel-iron slag to ferrosilicon slag is determined by the mass ratio of Cr2O3 and Mn2O3 contained in the nickel-iron slag and ferrosilicon slag. In this invention, the total amount of the two types of slag can reach about 60%, making full use of industrial waste and effectively reducing raw material costs. The decorative glass of this invention has excellent properties such as high mechanical strength, high hardness, and good corrosion resistance, with pure color and good decorative effect. The product can be made into decorative panels, etc., and can be widely used in building decoration materials, wear-resistant and corrosion-resistant materials, and craft ornaments.

Description

Technical Field

[0001] This invention relates to the field of colored glass preparation, specifically to a decorative glass based on metallurgical waste slag and its preparation process. Background Technology

[0002] Black decorative glass made from waste residue is an architectural and artistic glass material primarily produced from various metallurgical waste slags, tailings from mining operations, and fly ash from thermal power plants. Black glass is achieved by adding composite colorants to ordinary silicate glass, adjusting the absorption spectrum through the type and amount of colorants, and utilizing the principle of complementary colors.

[0003] The production of black glass does not require high Fe2O3 content in raw materials, so industrial tailings, metallurgical slag, fly ash, etc. can be used as the main raw materials. Moreover, there is no pollution in the production process and the product itself has no radioactive pollution, making it a green material.

[0004] To date, there has been extensive research in China on the use of slag to manufacture black glass or microcrystalline glass. For example, Chongqing University of Architecture and Engineering has used waste chromium slag to manufacture black glass architectural panels (ZL90106159.X); Wuhan University of Technology has used yellow phosphorus slag and tantalum-niobium tailings to manufacture black glass products (Chinese patent application number 200610019268.5); and Dalian University of Technology has used manganese-iron slag to prepare black microcrystalline glass (Chinese patent ZL200910187259.0). However, these existing technologies use a relatively small proportion of waste materials, still failing to achieve the goal of using large amounts of waste slag for black glass production. Furthermore, they require the addition of Cr2O3 and Mn2O3 as colorants, which does not reduce the production cost of black glass. Summary of the Invention

[0005] The purpose of this invention is to develop a black decorative glass based on metallurgical waste slag and its preparation process. By utilizing the existing components in the metallurgical waste slag and adjusting the component ratio, a black decorative glass with better color can be obtained without adding additional colorants.

[0006] The above-mentioned technical objective of the present invention is achieved through the following technical solution:

[0007] This invention provides a decorative glass based on metallurgical waste slag, wherein the raw materials for preparing the decorative glass include nickel-iron slag and ferrosilicon slag;

[0008] The mass ratio of nickel-iron slag to ferrosilicon slag is determined by the mass ratio of Cr2O3 and Mn2O3 contained in the nickel-iron slag and ferrosilicon slag and the design glass composition. That is, the specific mass percentage of Cr2O3 and Mn2O3 is determined, and the amount of waste slag is calculated based on the Cr2O3 and Mn2O3 contained in the nickel-iron slag and ferrosilicon slag.

[0009] Furthermore, in this invention, the specific mass percentages of Cr2O3 and Mn2O3 are determined based on the absorption spectrum.

[0010] In this invention, the mass percentages of Cr2O3 and Mn2O3 are adjusted using absorption spectroscopy to obtain decorative glass with higher black purity. Furthermore, the amount of nickel-iron slag and ferrosilicon slag added is adjusted by adjusting the mass percentages of Cr2O3 and Mn2O3, which not only enables the simultaneous recycling of nickel-iron slag and ferrosilicon slag, but also significantly improves the flexural strength and hardness of the decorative glass.

[0011] Nickel-iron slag contains SiO2, Al2O3, MgO, Cr2O3, and Fe2O3, while ferrosilicon slag contains not only SiO2, Al2O3, and CaO, but also Mn2O3. By combining nickel-iron slag and ferrosilicon slag, the principle of composite spectral absorption of Cr2O3, Fe2O3, and Mn2O3 can be applied to obtain black glass with better color without the addition of additional colorants. At the same time, it ensures that the black glass has good mechanical properties and chemical stability.

[0012] Furthermore, the mass ratio of Cr2O3 to Mn2O3 is (0.3–1):(3–7.5). When the proportions of Cr2O3 and Mn2O3 in the composition of black glass meet the above ratio, black color can be obtained by combining the brownish-red color formed by Mn2O3 and Fe2O3 with the green color of Cr2O3. At the same time, the amount of waste residue used in the preparation of black glass can be increased, thereby further achieving the goal of saving resources and avoiding pollution of the environment by nickel-iron slag.

[0013] Furthermore, according to weight parts, the black glass comprises the following components (wt%): 45-55 parts SiO2, 2.5-6 parts Fe2O3, 4.5-10 parts Al2O3, 4-8.5 parts CaO, 7-20 parts MgO, 10-16 parts Na2O, 0.4-1 part K2O, 3-7.5 parts Mn2O3, and 0.3-1 part Cr2O3.

[0014] Furthermore, calculated by weight, the nickel-iron slag comprises the following components: 40-50 parts SiO2, 5-12 parts Fe2O3, 4-9 parts Al2O3, 1-10 parts CaO, 20-38 parts MgO, 0.2-2 parts K2O, 0-1 parts Na2O, 1-3 parts Cr2O3, 0.2-0.8 parts Mn2O3, and 0-0.2 parts loss on ignition.

[0015] Furthermore, calculated by weight, the main components of the ferrosilicon slag are as follows: SiO2 40-55 parts, Fe2O3 1-3 parts, Al2O3 9-18 parts, CaO 15-22 parts, MgO 2-8 parts, K2O 0.5-3 parts, Na2O 0.5-3 parts, Mn2O3 8-16 parts, and loss on ignition components 0-1 parts.

[0016] Furthermore, the raw materials for preparing the decorative glass, calculated by weight, include the following components: 10-50 parts of nickel-iron slag, 20-48 parts of ferrosilicon slag, 10-25 parts of silica powder, 15-26 parts of soda ash, and 0.5-2 parts of sodium sulfate.

[0017] The present invention also provides a process for preparing decorative glass based on metallurgical waste slag, which has the same technical effect.

[0018] The present invention provides a process for preparing decorative glass based on metallurgical waste slag, comprising the following steps:

[0019] To obtain the composition of nickel-iron slag and ferrosilicon slag;

[0020] The raw material ratio is determined based on the composition of nickel-iron slag and ferrosilicon slag;

[0021] Prepare ingredients according to the determined raw material ratio;

[0022] After the raw materials are mixed evenly, add them and melt them.

[0023] The melt is injected into a mold to form the shape;

[0024] Annealing, followed by furnace cooling;

[0025] The black decorative glass is obtained by cold processing.

[0026] Furthermore, the melting temperature is 1420–1480℃.

[0027] Furthermore, the annealing temperature is 550–700℃.

[0028] In summary, the present invention has the following beneficial effects:

[0029] In this invention, the total amount of the two types of slag can reach about 60%, making full use of industrial waste and effectively reducing raw material costs. The black glass of this invention has excellent properties such as high mechanical strength, high hardness, and good corrosion resistance, with pure color and good decorative effect. The product can be made into various pipes, plates, etc., and can be widely used in wear-resistant and corrosion-resistant materials for construction, building decoration materials, handicrafts, chemical corrosion-resistant equipment, and kitchenware materials, etc. Detailed Implementation

[0030] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the specific implementation methods, features and effects of a decorative glass based on metallurgical waste slag and its preparation process according to the present invention are described in detail below.

[0031] The materials used in this specific implementation method are from the following sources:

[0032] Nickel-iron slag: Dalian Fuli Nickel-based New Materials Co., Ltd., particle size 40-60 mesh;

[0033] Silicomanganese slag: CITIC Jinzhou Ferroalloy Co., Ltd., particle size 40-60 mesh;

[0034] Silica powder: Xiang Sheng Building Materials Sales Co., Ltd., Fengyang County, Anhui Province; SiO2>98%;

[0035] Soda ash: Shandong Haihua Co., Ltd. Soda ash plant, industrial grade;

[0036] Glauber's salt: Shandong Aochuang Chemical Co., Ltd., industrial grade;

[0037] The specific embodiment provides a method for preparing decorative glass based on metallurgical waste slag, which includes nickel-iron slag and ferrosilicon slag.

[0038] The mass ratio of nickel-iron slag to ferrosilicon slag is determined by the mass ratio of Cr2O3 and Mn2O3 contained in the nickel-iron slag and ferrosilicon slag, wherein the preferred mass ratio of Cr2O3 to Mn2O3 is (0.3~1):(1.6~7.5).

[0039] To obtain decorative glass with better color, the decorative glass provided in this specific embodiment includes the following components by mass percentage: SiO2 45-55 parts, Fe2O3 2.5-6 parts, Al2O3 4.5-10 parts, CaO 4-8.5 parts, MgO 7-20 parts, Na2O 10-16 parts, K2O 0.4-1 part, Mn2O3 3-7.5 parts, and Cr2O3 0.3-1 part.

[0040] According to the weight parts, the nickel-iron slag selected in this specific embodiment includes the following components: 40-50 parts SiO2, 5-12 parts Fe2O3, 4-9 parts Al2O3, 1-10 parts CaO, 20-38 parts MgO, 0.2-2 parts K2O, 0-1 parts Na2O, 1-3 parts Cr2O3, 0.2-0.8 parts Mn2O3, and 0-0.2 parts loss on ignition.

[0041] Based on weight parts, the main components of the ferrosilicon slag selected in this specific embodiment are as follows: SiO2 40-55 parts, Fe2O3 1-3 parts, Al2O3 9-18 parts, CaO 15-22 parts, MgO 2-8 parts, K2O 0.5-3 parts, Na2O 0.5-3 parts, Mn2O3 8-16 parts, and loss on ignition components 0-1 parts.

[0042] Based on the above-mentioned composition of nickel-iron slag and ferrosilicon slag, in order to obtain black glass with better color, the raw materials selected in this specific embodiment, calculated by weight, include the following components: 10-50 parts of nickel-iron slag, 20-48 parts of ferrosilicon slag, 10-25 parts of silica powder, 15-26 parts of soda ash, and 0.5-2 parts of sodium sulfate.

[0043] This specific embodiment also provides a process for preparing decorative glass based on metallurgical waste slag, including the following steps:

[0044] S1. Obtain the composition of nickel-iron slag and ferrosilicon slag;

[0045] S2. Determine the raw material ratio based on the composition of nickel-iron slag and ferrosilicon slag;

[0046] S3. Prepare the ingredients according to the determined raw material ratio;

[0047] S4. After the raw materials are mixed evenly, add them and melt them;

[0048] S5. Pour the melt into the mold to form the shape;

[0049] S6. Annealing, followed by furnace cooling;

[0050] S7. The decorative glass is obtained by cold processing.

[0051] The melting temperature is 1420–1480℃; the annealing temperature is 560–620℃.

[0052] Example 1

[0053] This embodiment 1 provides a decorative glass based on metallurgical waste slag. The mass ratio of Cr2O3 to Mn2O3 is determined to be 0.75:5.5. The weight ratio of nickel-iron slag and ferrosilicon slag is calculated as follows: 38 parts nickel-iron slag and 35 parts ferrosilicon slag. Other raw materials are: 15.7 parts silica powder, 18.7 parts soda ash, and 1 part sodium sulfate.

[0054] The composition of each raw material, calculated by weight, is shown in the table below.

[0055] Table 1. Chemical composition (wt) of various raw materials in Example 1

[0056]

[0057]

[0058] The composition (mass percentage) of the decorative glass prepared based on the above raw material composition and proportion is shown in the table below.

[0059] Table 2. Chemical composition (wt) of the decorative glass in Example 1

[0060]

[0061] The preparation process of decorative glass based on metallurgical waste slag provided in Example 1 includes the following steps:

[0062] S1. The composition of nickel-iron slag and ferrosilicon slag was obtained, and the results are shown in Table 1.

[0063] S2. Determine the raw material ratio based on the composition of nickel-iron slag and ferrosilicon slag;

[0064] S3. Prepare the ingredients according to the determined raw material ratio;

[0065] S4. After mixing the raw materials evenly, add them; melt at a temperature of 1460℃ and hold for 3 hours to completely melt the glass raw materials and eliminate bubbles;

[0066] S5. Pour the melt into a steel mold to form the shape;

[0067] S6. After molding, transfer to an annealing furnace and anneal at 610℃ for 30 minutes, then cool with the furnace.

[0068] S7. Cold processing: The obtained decorative glass sample is cut, ground and polished to obtain the finished product.

[0069] Example 2

[0070] This embodiment 2 provides a decorative glass based on metallurgical waste slag. The ratio of Cr2O3 to Mn2O3 is determined to be 0.9:3.3. The mass ratio of nickel-iron slag and ferrosilicon slag is calculated as follows: nickel-iron slag 45.35 parts, ferrosilicon slag 20.2 parts. Other raw materials are: silica powder 22 parts, soda ash 21.3 parts, and sodium sulfate 1 part.

[0071] The composition of each raw material, calculated by weight, is shown in the table below.

[0072] Table 3. Chemical composition (wt) of various raw materials in Example 2

[0073]

[0074] The chemical composition (mass percentage) of the decorative glass prepared based on the above raw material composition and proportion is shown in the table below.

[0075] Table 4. Chemical composition (wt) of the decorative glass in Example 2

[0076]

[0077] The preparation process of decorative glass based on metallurgical waste slag provided in this embodiment 2 includes the following steps:

[0078] S1. The composition of nickel-iron slag and ferrosilicon slag was obtained, and the results are shown in Table 3.

[0079] S2. Determine the raw material ratio based on the composition of nickel-iron slag and ferrosilicon slag;

[0080] S3. Prepare the ingredients according to the determined raw material ratio;

[0081] S4. After mixing the raw materials evenly, add them; melt at 1480℃ and hold for 2 hours to completely melt the glass raw materials and eliminate bubbles;

[0082] S5. Pour the melt into a steel mold to form the shape;

[0083] S6. After molding, transfer to an annealing furnace and anneal at 700℃ for 30 minutes, then cool with the furnace.

[0084] S7. Cold processing: The obtained decorative glass sample is cut, ground and polished to obtain the finished product.

[0085] Example 3

[0086] This embodiment 3 provides a decorative glass based on metallurgical waste slag. The mass ratio of Cr2O3 to Mn2O3 is determined to be 0.4:7.2. The mass ratio of nickel-iron slag and ferrosilicon slag is calculated as follows: nickel-iron slag 20.15 parts, ferrosilicon slag 46.96 parts. Other raw materials are: silica powder 20.6 parts, soda ash 21 parts, and sodium sulfate 1 part.

[0087] The composition of each raw material, calculated by weight, is shown in the table below.

[0088] Table 5. Chemical composition of various raw materials in Example 3

[0089]

[0090] The chemical composition (mass percentage) of the decorative glass prepared based on the above raw material composition and proportion is shown in the table below.

[0091] Table 6. Chemical composition of the decorative glass in Example 3

[0092]

[0093] The preparation process of decorative glass based on metallurgical waste slag provided in this embodiment 3 includes the following steps:

[0094] S1. The composition of nickel-iron slag and ferrosilicon slag was obtained, and the results are shown in Table 5.

[0095] S2. Determine the raw material ratio based on the composition of nickel-iron slag and ferrosilicon slag;

[0096] S3. Prepare the ingredients according to the determined raw material ratio;

[0097] S4. After mixing the raw materials evenly, add the materials; melt at 1450℃ and hold for 3 hours to completely melt the glass raw materials and eliminate bubbles;

[0098] S5. Pour the melt into a steel mold to form the shape;

[0099] S6. After molding, transfer to an annealing furnace and anneal at 600℃ for 30 minutes, then cool with the furnace.

[0100] S7. Cold processing: The obtained decorative glass sample is cut, ground and polished to obtain the finished product.

[0101] Comparative Example 1

[0102] Glass was prepared using only nickel-iron slag as the main raw material for color comparison. The raw materials were: 36 parts silica powder, 50 parts nickel-iron slag, 25 parts soda ash and 0.6 parts sodium sulfate.

[0103] The chemical composition of each raw material, calculated by weight, is shown in the table below.

[0104] Table 7. Chemical composition (wt) of various raw materials in Comparative Example 1

[0105]

[0106] The composition (mass percentage) of the glass prepared according to the above-mentioned raw material composition and proportion is shown in the table below.

[0107] Table 8. Chemical composition of glass in Comparative Example 1

[0108]

[0109] The glass preparation process based on metallurgical waste slag provided in Comparative Example 1 includes the following steps:

[0110] S1. The composition of nickel-iron slag was obtained, and the results are shown in Table 7.

[0111] S2. Determine the raw material ratio based on the composition of nickel-iron slag and ferrosilicon slag;

[0112] S3. Prepare the ingredients according to the determined raw material ratio;

[0113] S4. After mixing the raw materials evenly, add the materials; melt at a temperature of 1460℃ and hold for 2 hours to completely melt the glass raw materials and eliminate bubbles;

[0114] S5. Pour the melt into a steel mold to form the shape;

[0115] S6. After molding, transfer to an annealing furnace and anneal at 560℃ for 30 minutes, then cool with the furnace.

[0116] S7. Cold processing: The obtained decorative glass sample is cut, ground and polished to obtain the finished product.

[0117] Comparative Example 2

[0118] Glass was prepared using only ferrosilicon slag as the main raw material for color comparison. The raw materials were: 42.2 parts silica powder, 45 parts ferrosilicon slag, 23.3 parts soda ash and 1 part sodium sulfate.

[0119] The chemical composition of each raw material, calculated by weight, is shown in the table below.

[0120] Table 9. Chemical composition (wt) of various raw materials in Comparative Example 2

[0121]

[0122] The composition (mass percentage) of the glass prepared according to the above-mentioned raw material composition and proportion is shown in the table below.

[0123] Table 10. Chemical composition of glass in Comparative Example 2

[0124]

[0125] The glass preparation process based on metallurgical waste slag provided in Comparative Example 2 includes the following steps:

[0126] S1. The composition of nickel-iron slag was obtained, and the results are shown in Table 9.

[0127] S2. Determine the raw material ratio based on the composition of the ferrosilicon manganese slag;

[0128] S3. Prepare the ingredients according to the determined raw material ratio;

[0129] S4. After mixing the raw materials evenly, add them; melt at 1450℃ and hold for 2 hours to completely melt the glass raw materials and eliminate bubbles;

[0130] S5. Pour the melt into a steel mold to form the shape;

[0131] S6. After molding, transfer to an annealing furnace and anneal at 550℃ for 30 minutes, then cool with the furnace.

[0132] S7. Cold processing: The obtained decorative glass sample is cut, ground and polished to obtain the finished product.

[0133] Performance testing

[0134] The decorative glass obtained in Examples 1-3 was tested for flexural strength, microhardness, water resistance and thermal expansion curve. The results are shown in Table 11.

[0135] Test methods

[0136] 1. Flexural strength test: The flexural strength of the samples was determined by the three-point bending method using an MC009-wds10M electronic universal material performance testing machine. Six strip samples (8mm×6mm×80mm) were tested, the flexural strength was calculated, and the average value was finally calculated.

[0137] 2. Microhardness determination: The hardness of the sample is determined using a digital microhardness tester. Three points are measured for each sample, and the average value is used to represent its microhardness. A total of three samples are measured, and the average value of the microhardness of the three samples is calculated.

[0138] 3. Water resistance test: The powder immersion loss method (DTN12116) was used for determination. The sample was crushed, and 2 grams of decorative glass powder (40 mesh lower and 60 mesh upper) was placed in a 50 ml volumetric flask. Water was added to the mark, and the flask was kept at 98±0.5℃ for 60 minutes. The water resistance at 100 cm was then measured. 2 Weight loss rate (mg / 100cm) 2 ).

[0139] 4. Thermal expansion curve determination: The thermal expansion curve of the glass sample was determined using a PCY-1200 quartz dilatometer to determine the linear expansion coefficient and characteristic temperature T of the glass. g and T f .

[0140] Table 11. Performance Test Results

[0141]

[0142] According to the test results above, the decorative glass provided by the present invention uses a combination of nickel-iron slag and silicon-manganese slag. Compared with the use of nickel-iron slag or silicon-manganese slag alone, the decorative glass obtained has higher black purity and higher bending resistance and hardness.

[0143] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been shown above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A decorative glass based on metallurgical waste slag, characterized in that, The mass percentages of Cr2O3 and Mn2O3 are adjusted according to the absorption spectrum. Then, the raw material ratio is adjusted so that the mass ratio of nickel-iron slag and ferrosilicon slag in the batch is determined according to the determined mass ratio of Cr2O3 and Mn2O3 and the mass percentages of Cr2O3 and Mn2O3 contained in the nickel-iron slag and ferrosilicon slag. The mass ratio of Cr2O3 to Mn2O3 is (0.3~1):(3~7.5); The raw materials for preparing the decorative glass, calculated by weight, include the following components: 10-50 parts of nickel-iron slag, 20-48 parts of ferromanganese slag, 10-25 parts of silica powder, 15-26 parts of soda ash, and 0.5-2 parts of sodium sulfate. The decorative glass comprises the following components by weight percentage: SiO2 45~55%, Fe2O3 2.5~6%, Al2O3 4.5~10%, CaO 4~8.5%, MgO 7~20%, Na2O 10~16%, K2O 0.4~1%, Mn2O3 3~7.5%, and Cr2O3 0.3~1%.

2. The decorative glass based on metallurgical waste slag according to claim 1, characterized in that, The nickel-iron slag comprises the following components by weight percentage: SiO2 40-50%, Fe2O3 5-12%, Al2O3 4-9%, CaO 1-10%, MgO 20-38%, K2O 0.2-2%, Na2O 0-1%, Cr2O3 1-3%, Mn2O3 0.2-0.8%, and loss on ignition components 0-0.2%.

3. The decorative glass based on metallurgical waste slag according to claim 1, characterized in that, The main components of ferrosilicon slag, calculated by weight percentage, are: SiO2 40~55%, Fe2O3 1~3%, Al2O3 9~18%, CaO 15~22%, MgO 2~8%, K2O 0.5~3%, Na2O 0.5~3%, Mn2O3 8~16%, and loss on ignition components 0~1%.

4. The preparation process of decorative glass based on metallurgical waste slag according to any one of claims 1 to 3, characterized in that, The following steps are included: To obtain the composition of nickel-iron slag and ferrosilicon slag; The raw material ratio is determined based on the composition of nickel-iron slag and ferrosilicon slag; Prepare ingredients according to the determined raw material ratio; After the raw materials are mixed evenly, add them and melt them. The melt is injected into a mold to form the shape; Annealing, followed by furnace cooling; The decorative glass is obtained through cold processing.

5. The preparation process of decorative glass based on metallurgical waste slag according to claim 4, characterized in that, The melting temperature is 1420~1480℃.

6. The preparation process of decorative glass based on metallurgical waste slag according to claim 4, characterized in that, The annealing temperature is 550~700℃.

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