Preparation method of porous glass ceramic
Through the method of specific raw material ratio and temperature-controlled calcination, the problem of unstable quality of porous glass ceramic products is solved, and the resource utilization of waste incineration fly ash and fly ash is realized, and porous glass ceramics with excellent performance are prepared, which are suitable for multiple fields.
Patent Information
- Application Number
- CN202510109342.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-23
- Publication Date
- 2025-07-18
AI Technical Summary
The prior art is difficult to accurately control the pore structure and performance, resulting in unstable quality of porous glass ceramic products, and the production process requires expensive additives or complex equipment, which increases production costs and limits its large-scale application.
Porous substrates are prepared by raw materials such as polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, nitric acid and aluminum isopropoxide. Porous glass ceramics are prepared by combining waste incineration fly ash, fly ash, glass powder and porous diatomaceous earth, and mixing and temperature-controlled calcination in specific proportions.
Resource utilization of waste incineration fly ash and fly ash is realized, environmental pollution is reduced, porous glass ceramics with excellent performance are prepared, suitable for multiple fields, and the specific surface area and insulation properties of the material are improved.
Smart Images
Figure CN120328840A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of the preparation of porous ceramics, and particularly relates to a method for preparing porous glass ceramics. Background Art
[0002] Waste incineration fly ash, as a by-product generated during the waste incineration process, contains a large amount of heavy metals and harmful substances such as dioxins. If not properly treated, it will cause serious pollution to the soil, water body and atmosphere, and thus threaten the health of humans and the balance of the ecosystem. At present, the main methods for treating fly ash include landfill and solidification / stabilization treatment, but these methods have problems such as occupying a large amount of land resources and possibly causing secondary pollution. Fly ash is a solid waste generated after coal combustion. A large amount of accumulation will not only occupy land, but also generate dust and cause air pollution. The traditional treatment method is to use it for the preparation of rough building materials, and this method has a low added value.
[0003] Porous glass ceramics is a material with special properties. Using waste to prepare porous glass ceramics conforms to the concept of resource recycling and sustainable development. It can not only reduce the dependence on natural resources, but also reduce environmental pollution. However, there are still some deficiencies in the current preparation of porous glass ceramics using waste incineration fly ash and fly ash. From a technical perspective, the existing preparation methods are difficult to precisely control the pore structure and properties, resulting in unstable product quality; in terms of cost, some preparation methods require the use of expensive additives or rely on complex equipment, which undoubtedly increases the production cost and limits its large-scale application.
[0004] In summary, developing a new preparation method for porous glass ceramics with a simple process has important practical significance and broad application prospects. Summary of the Invention
[0005] The purpose of the present invention is to provide a method for preparing porous glass ceramics in view of the deficiencies of the prior art.
[0006] In order to achieve the above purpose, the technical solution of the present invention is as follows:
[0007] A method for preparing porous glass ceramics, comprising:
[0008] Step S1, preparing a porous substrate; specifically:
[0009] Dissolve poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (P123) in an anhydrous ethanol solvent to obtain solution A;
[0010] Dissolve nitric acid in an anhydrous ethanol solvent, and then add aluminum isopropoxide to obtain solution B;
[0011] After mixing solution A and solution B evenly, add Mg(NO3)·6H2O and stir well to obtain the porous substrate C;
[0012] Step S2: Mix the waste incineration fly ash, fly ash, porous substrate C, glass powder, and porous diatomite powder evenly, let it stand for a period of time and then dry it to obtain the mixture D;
[0013] Step S3: Take an appropriate amount of the mixture D and place it in a reaction vessel, and calcine it at a temperature of 800-1200°C in an air atmosphere to obtain the porous glass ceramic.
[0014] Preferably, in step S1, the mass-volume ratio of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer to nitric acid is 2 g:(3-3.2) mL.
[0015] Preferably, in step S1, the mass ratio of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer to aluminum isopropoxide is 2:(4-4.08).
[0016] Preferably, in step S1, the mass ratio of Mg element in Mg(NO3)·6H2O to Al2O3 in the porous glass ceramic is 1:(10-20).
[0017] Preferably, in step S2, the mass ratio of the waste incineration fly ash, fly ash, glass powder, porous diatomite, and porous substrate C is 1:(1-2):(0.5-2):(0.5-1):(0.05-0.3).
[0018] Preferably, in step S3, at a heating rate of 5-10°C·min -1 to 900-1200°C.
[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0020] 1. The present invention prepares porous glass ceramics from waste incineration fly ash and fly ash. The raw materials, waste incineration fly ash and fly ash, are solid wastes. Through this invention, their resource utilization can be realized, environmental pollution is reduced, and raw material resources are saved at the same time.
[0021] 2. The present invention prepares porous glass ceramics from waste incineration fly ash and fly ash. Fly ash is rich in resources such as silicon oxide and aluminum oxide. These elements contribute to the sintering of porous glass ceramics, and porous fly ash is conducive to the formation of porous pores in the preparation process of glass ceramics.
[0022] 3. The porous glass-ceramics of the present invention are prepared from municipal solid waste incineration fly ash and fly ash. When Mg(NO3)2·6H2O is added to the mixed solution, Mg ions can serve as the support and stabilizer for the porous structure, which helps to improve the structural stability and porosity of the porous substrate C.
[0023] 4. By controlled-temperature calcination, the porous glass-ceramics prepared from municipal solid waste incineration fly ash and fly ash have a porous structure, which increases the specific surface area of the material and is beneficial to applications such as adsorption and catalysis. The porous structure can also improve the heat insulation and thermal insulation properties of the material and reduce the density of the material.
[0024] 5. The porous glass-ceramics of the present invention are prepared from municipal solid waste incineration fly ash and fly ash. A new preparation process is adopted, and through specific raw material ratios and sintering conditions, porous glass-ceramics with excellent properties are successfully prepared.
[0025] 6. The porous glass-ceramics prepared from municipal solid waste incineration fly ash and fly ash of the present invention have a variety of excellent properties and are easy to process. They can be easily cut, ground, coated, etc., and can be applied in multiple fields. Description of the Drawings
[0026] Figure 1 SEM image of the porous glass-ceramics prepared in Example 1 at a magnification of 10k.
[0027] Figure 2 SEM image of the porous glass-ceramics prepared in Example 1 at a magnification of 6k.
[0028] Figure 3 SEM images of the porous glass-ceramics prepared in the comparative example at different scales; (a), (b), and (c) are SEM images of the porous glass-ceramics in Comparative Example 6 at magnifications of 1.5k, 2k, and 2.5k respectively, and (d), (e), and (f) are SEM images of the porous glass-ceramics in Comparative Example 8 at magnifications of 1k, 2k, and 2.5k respectively. Detailed Embodiments
[0029] The following further analyzes the present invention in combination with specific embodiments.
[0030] Example 1
[0031] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain solution A.
[0032] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, and then add 4.08 g of aluminum isopropoxide to obtain solution B.
[0033] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring evenly, cover with a plastic wrap to obtain a porous substrate C.
[0034] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: diatomite = 1:1:1:0.05:0.5, mix evenly, let stand for 24 h, and dry in an oven at 60 °C.
[0035] (5) Finally, take an appropriate amount of the block and place it in a crucible, heat it at a rate of 10 °C per minute, and calcine it at 900 °C in an air atmosphere for 2 h to obtain a porous glass ceramic.
[0036] Example 2
[0037] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain solution A.
[0038] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, and then add 4.08 g of aluminum isopropoxide to obtain solution B.
[0039] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring evenly, cover with a plastic wrap to obtain a porous substrate C.
[0040] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: diatomite = 1:1:1:0.1:0.5, mix evenly, let stand for 24 h, and dry in an oven at 60 °C.
[0041] (5) Finally, take an appropriate amount of the block and place it in a crucible, heat it at a rate of 10 °C per minute, and calcine it at 1200 °C in an air atmosphere for 2 h to obtain a porous glass ceramic.
[0042] Example 3
[0043] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain solution A.
[0044] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, and then add 4.08 g of aluminum isopropoxide to obtain solution B.
[0045] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring evenly, cover with a plastic wrap to obtain a porous substrate C.
[0046] (4) Mix thoroughly according to the mass ratio of fly ash: fly-ash powder: glass powder: substrate C: diatomite = 1:1:1:0.03:0.5, let stand for 24 h, and dry in an oven at 60 °C.
[0047] (5) Finally, take an appropriate amount of the block and place it in a crucible, heat it at a rate of 10 °C per minute, and calcine it at 900 °C for 2 h in an air atmosphere to obtain porous glass ceramics.
[0048] Example 4
[0049] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain solution A.
[0050] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, and then add 4.08 g of aluminum isopropoxide to obtain solution B.
[0051] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring thoroughly; cover with a plastic wrap to obtain porous substrate C.
[0052] (4) Mix thoroughly according to the mass ratio of fly ash: fly-ash powder: glass powder: substrate C: diatomite = 1:1:1:0.03:0.5, let stand for 24 h, and dry in an oven at 60 °C.
[0053] (5) Finally, take an appropriate amount of the block and place it in a crucible, heat it at a rate of 10 °C per minute, and calcine it at 1130 °C for 0.5 h in an air atmosphere to obtain porous glass ceramics.
[0054] Comparative Example 1
[0055] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain solution A.
[0056] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, and then add 4.08 g of aluminum isopropoxide to obtain solution B.
[0057] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring thoroughly; cover with a plastic wrap to obtain porous substrate C.
[0058] (4) Mix thoroughly according to the mass ratio of fly ash: fly-ash powder: glass powder: substrate C: feldspar powder = 1:1:1:0.3:0.5, let stand for 24 h, and dry in an oven at 60 °C.
[0059] (5) Finally, take an appropriate amount of the block and place it in a crucible. Heat it at a rate of 10 °C per minute and calcine it at 900 °C for 2 h in an air atmosphere to obtain porous glass ceramics.
[0060] Comparative Example 2
[0061] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain Solution A.
[0062] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, then add 4.08 g of aluminum isopropoxide to obtain Solution B.
[0063] (3) Mix A and B evenly, then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring well; cover it with plastic wrap to obtain porous substrate C.
[0064] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: black talc = 1:1:1:0.3:0.5, mix them evenly, let it stand for 24 h, and dry it in an oven at 60 °C.
[0065] (5) Finally, take an appropriate amount of the block and place it in a crucible. Heat it at a rate of 10 °C per minute and calcine it at 900 °C for 2 h in an air atmosphere to obtain porous glass ceramics.
[0066] Comparative Example 3
[0067] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain Solution A.
[0068] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, then add 4.08 g of aluminum isopropoxide to obtain Solution B.
[0069] (3) Mix A and B evenly, then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring well; cover it with plastic wrap to obtain porous substrate C.
[0070] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: attapulgite = 1:1:1:0.3:0.5, mix them evenly, let it stand for 24 h, and dry it in an oven at 60 °C.
[0071] (5) Finally, take an appropriate amount of the block and place it in a crucible. Heat it at a rate of 10 °C per minute and calcine it at 900 °C for 2 h in an air atmosphere to obtain porous glass ceramics.
[0072] Comparative Example 4
[0073] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain Solution A.
[0074] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol. Then add 4.08 g of aluminum isopropoxide to obtain Solution B.
[0075] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring well; cover it with plastic wrap to obtain the porous substrate C.
[0076] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: halloysite = 1:1:1:0.3:0.5, mix them evenly, let it stand for 24 h, and dry it in an oven at 60 °C.
[0077] (5) Finally, take an appropriate amount of the block and place it in a crucible. Heat it at a rate of 10 °C per minute, and calcine it in an air atmosphere at 900 °C for 2 h to obtain the porous glass ceramic.
[0078] Comparative Example 5
[0079] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain Solution A.
[0080] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol. Then add 4.08 g of aluminum isopropoxide to obtain Solution B.
[0081] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring well; cover it with plastic wrap to obtain the porous substrate C.
[0082] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: diatomite = 1:1:1:0.3:0.5, mix them evenly, let it stand for 24 h, and dry it in an oven at 60 °C.
[0083] (5) Finally, take an appropriate amount of the block and place it in a crucible. Heat it at a rate of 10 °C per minute, and calcine it in an air atmosphere at 900 °C for 2 h to obtain the porous glass ceramic.
[0084] Comparative Example 6
[0085] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain Solution A.
[0086] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol. Then add 4.08 g of aluminum isopropoxide to obtain Solution B.
[0087] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring evenly, cover it with plastic wrap to obtain the porous substrate C.
[0088] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: diatomite = 1:1:1:0.6:0.5, mix evenly, let stand for 24 h, and dry in an oven at 60 °C.
[0089] (5) Finally, take an appropriate amount of the block and place it in a crucible, heat it up at a rate of 10 °C per minute, and calcine it at 900 °C in an air atmosphere for 2 h to obtain the porous glass ceramic.
[0090] Comparative Example 7
[0091] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain solution A.
[0092] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, and then add 4.08 g of aluminum isopropoxide to obtain solution B.
[0093] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring evenly, cover it with plastic wrap to obtain the porous substrate C.
[0094] (4) According to the mass ratio of fly ash: fly ash: glass powder: substrate C: diatomite = 1:1:1:0.1:0.5, mix evenly, let stand for 24 h, and dry in an oven at 60 °C.
[0095] (5) Finally, take an appropriate amount of the block and place it in a crucible, heat it up at a rate of 10 °C per minute, and calcine it at 900 °C in an air atmosphere for 2 h to obtain the porous glass ceramic.
[0096] Comparative Example 8
[0097] (1) Weigh 2 g of P123 and dissolve it in a 20 mL beaker of anhydrous ethanol to obtain solution A.
[0098] (2) Measure 3.2 mL of nitric acid and dissolve it in another 20 mL beaker of anhydrous ethanol, and then add 4.08 g of aluminum isopropoxide to obtain solution B.
[0099] (3) Mix A and B evenly, and then add 1.1 g of Mg(NO3)·6H2O (the theoretical mass ratio of Mg / Al2O3 = 10%); after stirring evenly, cover it with plastic wrap to obtain the porous substrate C.
[0100] (4) Mix evenly according to the mass ratio of fly ash: coal ash: glass powder: substrate C: diatomite = 1:1:1:0.3:0.5, let stand for 24 h, and dry in an oven at 60 °C.
[0101] (5) Finally, take an appropriate amount of the block and place it in a crucible, heat it at a rate of 10 °C per minute, and calcine it at 800 °C in an air atmosphere for 2 h to obtain porous glass ceramics.
[0102] Table 1 Reaction conditions and products of each example and comparative example
[0103]
[0104]
[0105] As can be seen from Table 1, the strength of Example 2 is the highest. The comparison between Example 1 and Comparative Example 6 shows that reducing the amount of substrate C will increase the strength of the porous glass ceramics. The comparison between Comparative Example 5 and Comparative Example 8 shows that for porous glass ceramics, increasing the calcination temperature will increase their strength. The comparison between Comparative Example 5 and Comparative Examples 1-4 shows that adding porous diatomite powder will increase the strength of the porous glass ceramics.
[0106] Referring to the preparation method of Example 1, according to the ratios in Table 2, the raw materials were adjusted to prepare Comparative Examples 9-14.
[0107] Table 2 Reaction conditions and products of each comparative example
[0108]
[0109] As can be seen from Table 2, without adding substrate C, the prepared ceramic body has sintering ability but lacks porosity.
[0110] From Figure 1 - Figure 2 and Figure 3 in (a)- Figure 3 in (f), compared with Comparative Examples 6 and 8, the micro-pores of the ceramic body in Example 1 are more significant.
[0111] The above is the preferred implementation mode of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and retouches can be made, and these improvements and retouches are also regarded as the protection scope of the present invention.
Claims
1. A preparation method of a porous glass-ceramic, characterized in that, The method comprises: Step S1, preparing a porous substrate; specifically: Dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in an anhydrous ethanol solvent to obtain a solution A; Dissolve nitric acid in anhydrous ethanol solvent, and then add aluminum isopropoxide to obtain solution B; After the solution A and the solution B are mixed evenly, Mg(NO3)·6H2O is added and stirred evenly to obtain a porous substrate C; Step S2, mixing the waste incineration fly ash, fly ash, porous substrate C, glass powder, and porous diatomaceous earth powder, standing for a period of time, and then drying to obtain a mixture D; Step S3: taking a proper amount of mixture D and placing it in a reaction container, and calcining it at a temperature of 900-1200° C. in an air atmosphere to obtain a porous glass ceramic.
2. The method according to claim 1, wherein In step S1, the mass volume ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to nitric acid is 2 g: (3-3.2) mL.
3. The method according to claim 1, wherein In step S1, the mass ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to aluminum isopropoxide is 2:(4-4.08).
4. The method according to claim 1, wherein In step S1, the mass ratio of Mg element in Mg(NO3)·6H2O to Al2O3 in the porous glass ceramic is 1:(10-20).
5. The method according to claim 1, wherein In step S2, the mass ratio of waste incineration fly ash, fly ash, glass powder, porous diatomaceous earth and porous substrate C is 1: (1-2): (0.5-2): (0.5-1): (0.05-0.3).
6. The method according to claim 1, characterized in that In step S3, the heating rate is 5 to 10 °C·min -1 to 900 to 1200 °C.