Method for resource utilization of hazardous waste glass slag

Abstract

The invention provides a method for resource utilization of hazardous waste glass slag. The method comprises the following steps: screening the hazardous waste glass slag according to particle sizes to obtain first particles, second particles, third particles and fourth particles; cement and water are mixed to prepare cement paste; mixing the first particles, the second particles and part of the third particles to obtain a first product; mixing the first product with cement paste, and curing to obtain a concrete product; mixing the remaining third particles with the fourth particles to obtain a second product, mixing the second product with fly ash, adding an alkaline activator, and uniformly mixing; and curing to obtain the geopolymer. Hazardous waste glass slag is divided into particles with different particle sizes in a grading screening mode, coarse particles, fine particles and part of superfine particle components are combined to form particle gradation, and a concrete product is manufactured; meanwhile, the high-strength geopolymer is prepared by utilizing the alkali reaction characteristic of the superfine particles.

Description

Technical Field

[0001] The present invention relates to the technical field of harmless and resource utilization of hazardous waste, and particularly to a method for resource utilization of hazardous waste glass slag. Background Art

[0002] Currently, the main harmless treatment technologies for hazardous waste include cement solidification and stabilization treatment, chemical agent treatment, incineration treatment, etc. These treatment methods have poor inhibitory / removal effects on hazardous factors such as heavy metals and organic matters in hazardous waste, and are prone to cause potential environmental risks. The vitrification technology rapidly decomposes the organic matters in hazardous waste through high-temperature treatment, and at the same time passivates components such as heavy metals into the silicon-oxygen lattice of glass. This technology has received more and more attention in recent years. However, there are few reports on the resource utilization of the product after the melting treatment of hazardous waste - glass slag.

[0003] The existing method for using hazardous waste glass slag to make building materials is: directly using hazardous waste glass slag to prepare concrete products or geopolymers; the compressive strengths of the concrete products and geopolymers prepared by this method are both relatively low.

[0004] Therefore, there is an urgent need to develop a method for resource utilization of hazardous waste glass slag, which can simultaneously improve the compressive strengths of the prepared concrete products and geopolymers. Summary of the Invention

[0005] The present invention provides a method for resource utilization of hazardous waste glass slag, which can achieve the technical effect of simultaneously improving the compressive strengths of the prepared concrete products and geopolymers.

[0006] The present invention provides a method for resource utilization of hazardous waste glass slag, comprising the following steps:

[0007] (1) Screening: Screening the hazardous waste glass slag according to particle size to obtain the first particle, the second particle, the third particle and the fourth particle; the particle size D1 of the first particle satisfies: D1≥4.75mm; the particle size D2 of the second particle satisfies: 0.3mm≤D2<4.75mm; the second particle includes the second particle M1, the second particle M2, the second particle M3, the second particle M4; the particle size of the second particle M1 satisfies: 2.36mm≤M1<4.75mm; the particle size of the second particle M2 satisfies: 1.18mm≤M2<2.36mm; the particle size of the second particle M3 satisfies: 0.6mm≤M3<1.18mm; the particle size of the second particle M4 satisfies: 0.3mm≤M4<0.6mm; the particle size D3 of the third particle satisfies: 0.15mm≤D3<0.3mm; the particle size D4 of the fourth particle satisfies: D4<0.15mm;

[0008] (2) Preparation of concrete product: Prepare a cement paste by mixing cement and water; Mix the first particles, the second particles, and part of the third particles to obtain a first product; Mix the first product with the cement paste and cure to obtain a concrete product.

[0009] (3) Preparation of geopolymer: Mix the remaining third particles and the fourth particles to obtain a second product, mix the second product with fly ash, and then add an alkaline activator and mix evenly; Cure to obtain a geopolymer.

[0010] The method as described above, wherein, in step (2), the mass ratio of the first product, cement, and water is 3:1:0.4 - 0.6.

[0011] The method as described above, wherein, in step (2), the mass ratio of the first particles, M1, M2, M3, M4, and the third particles in the first product is 0 - 10:10 - 15:10 - 25:20 - 31:20 - 30:5 - 15.

[0012] The method as described above, wherein, in step (2), during the mixing process of the cement and water, the stirring speed is 138 - 142 r / min;

[0013] and / or, during the mixing process of the first product and the cement paste, the stirring speed is 275 - 295 r / min.

[0014] The method as described above, wherein, in step (3), the alkaline activator includes a mixture of sodium hydroxide solution and water glass.

[0015] The method as described above, wherein, in the mixture, the concentration of the sodium hydroxide solution is 3 - 7.5 mol / L, and the mass ratio of the sodium hydroxide solution to water glass is (0.4 - 0.8):1.

[0016] The method as described above, wherein, in step (3), the mass ratio of the second product to the fly ash is (2 - 3):1.

[0017] The method as described above, wherein, in step (3), the total mass of the second product and the fly ash, and the alkaline activator are in a ratio of 1 g:(0.5 - 0.9) mL.

[0018] The method as described above, wherein, in step (3), in the second product, the mass ratio of the third particles to the fourth particles is 0 - 30:70 - 100.

[0019] The method as described above, wherein in step (3), during the mixing process of the second product and the fly ash, the stirring speed is 80 to 120 r / min;

[0020] and / or; during the mixing process after adding the alkaline activator, the stirring speed is 138 to 142 r / min.

[0021] The method for resource utilization of hazardous waste glass slag provided by the present invention divides the hazardous waste glass slag into particles with different particle sizes through a grading and screening method, combines the first particles, the second particles and part of the third particles to form a particle gradation, and manufactures concrete products; at the same time, making full use of the alkali reaction characteristics of the fourth particles, the fourth particles and the remaining third particles are used as raw materials to be compounded with an alkaline activator and fly ash, and geopolymers are prepared through a geopolymerization reaction. This method can give full play to the characteristics of particles with different particle sizes of hazardous waste glass slag, and at the same time manufacture concrete products and geopolymers with high compressive strength. Brief Description of the Drawings

[0022] Figure 1 It is a flow chart of the resource utilization of hazardous waste glass slag in the embodiment of the present invention. Detailed Embodiments

[0023] In order to make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0024] With the growth of the output of hazardous waste slag, the treatment of hazardous waste glass slag is urgent. When the prior art conducts resource treatment on hazardous waste glass slag, it is either directly used to prepare concrete products or directly used to prepare geopolymers. However, both the prepared concrete products and geopolymers have problems of insufficient strength.

[0025] The inventor has found through research that the particle size distribution of hazardous waste glass slag is relatively wide, and particles in different particle size ranges have different characteristics. Particle size is an important factor affecting reaction characteristics. When the particle size is below a certain level, the reaction performance of the particles will increase sharply. When the particle size is as small as a few microns or even nanometers, the surface energy of the particles will increase rapidly, resulting in a rapid increase in their reaction performance. For example, ultra-fine particles (i.e., particles with a particle size < 0.15 mm) will continue to react during curing, resulting in unstable concrete products and thus lower compressive strength. Coarse particles (i.e., particles with a particle size ≥ 0.3 mm) will reduce the efficiency of the geopolymerization reaction, resulting in poor compressive strength of the prepared geopolymer. Moreover, too many coarse particles may even prevent the formation of geopolymer.

[0026] Therefore, the present invention attempts to divide hazardous waste glass slag into multi-level particles according to particle size, and then carry out targeted reactions according to the characteristics of particles at different levels to improve the utilization effect of hazardous waste glass slag.

[0027] Based on the above analysis, the present invention attempts to screen hazardous waste glass slag into particles of different particle size levels by means of grading screening, and combine particles of different particle size levels to form an optimized particle gradation to produce high-strength concrete products. At the same time, particles of appropriate particle size are selected and compounded with an alkaline activator and fly ash to produce high-strength geopolymer through the geopolymerization reaction.

[0028] Based on this, the first aspect of the present invention provides a method for resource utilization of hazardous waste glass slag. The flow chart is shown in Figure 1 , and includes the following steps:

[0029] (1) Screening: Screening hazardous waste glass slag according to particle size to obtain first particles, second particles, third particles and fourth particles;

[0030] The particle size D1 of the first particles satisfies: D1 ≥ 4.75 mm;

[0031] The particle size D2 of the second particles satisfies: 0.3 mm ≤ D2 < 4.75 mm; The second particles include second particle M1, second particle M2, second particle M3, second particle M4; The particle size of the second particle M1 satisfies: 2.36 mm ≤ M1 < 4.75 mm; The particle size of the second particle M2 satisfies: 1.18 mm ≤ M2 < 2.36 mm; The particle size of the second particle M3 satisfies: 0.6 mm ≤ M3 < 1.18 mm; The particle size of the second particle M4 satisfies: 0.3 mm ≤ M4 < 0.6 mm;

[0032] The particle size D3 of the third particles satisfies: 0.15 mm ≤ D3 < 0.3 mm;

[0033] The particle size D4 of the fourth particles satisfies: D4 < 0.15 mm;

[0034] (2) Preparation of concrete products: Cement and water are mixed to form a cement paste; the first particles, the second particles, and a part of the third particles are mixed to obtain a first product; the first product is mixed with the cement paste and cured to obtain concrete products.

[0035] (3) Preparation of geopolymers: The remaining third particles and the fourth particles are mixed to obtain a second product, and after the second product is mixed with fly ash, an alkaline activator is added and mixed evenly; after curing, geopolymers are obtained.

[0036] Specifically, in step (1), after the hazardous waste glass slag is screened by particle size, the first particles, the second particles, the third particles, and the fourth particles with different particle size distributions are respectively obtained; and the second particles include second particle M1, second particle M2, second particle M3, and second particle M4; wherein, the range of the particle size D1 of the first particles is: D1≥4.75mm; the range of the particle size D2 of the second particles is: 0.3mm≤D2<4.75mm; the range of the particle size D3 of the third particles is: 0.15mm≤D3<0.3mm; the range of the particle size D4 of the fourth particles is: D4<0.15mm; the particle size of the second particle M1 satisfies: 2.36mm≤M1<4.75mm; the particle size of the second particle M2 satisfies: 1.18mm≤M2<2.36mm; the particle size of the second particle M3 satisfies: 0.6mm≤M3<1.18mm; the particle size of the second particle M4 satisfies: 0.3mm≤M4<0.6mm.

[0037] The present invention does not make specific limitations on the screening method, and only needs to meet the above screening effect. In one embodiment, coarse screening is first performed, and then fine screening is performed.

[0038] Further, the screen sizes of the coarse screening are 4.75mm, 2.36mm, and 1.18mm in sequence. The particles obtained after coarse screening are: the first particles, the second particle M1, and the second particle M2.

[0039] Further, during the screening process, the vibration amplitude is 1-3mm, for example, the vibration amplitude is 1mm, 1.5mm, 2mm, 2.5mm, or 3mm; preferably, the vibration amplitude is 1mm. The vibration frequency is 500-1000 times / min, for example, the vibration frequency is 500 times / min, 600 times / min, 700 times / min, 750 times / min, 800 times / min, 900 times / min, or 1000 times / min, preferably, the vibration frequency is 750 times / min. Within this range of vibration amplitude and vibration frequency, the screening effect is better.

[0040] Further, during the screening process, the screening residence time is 5 to 15 minutes, for example, the residence time is 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 12.5 minutes or 15 minutes. Within this residence time range, sufficient screening is ensured while reducing screen loss and energy consumption.

[0041] The second particles M2 are finely screened. The screen sizes for the fine screening are 0.6 mm, 0.3 mm, and 0.15 mm in sequence. The particles obtained after fine screening are: the second particles M3, the second particles M4, the third particles, and the fourth particles.

[0042] Further, during the screening process, the vibration amplitude is 60 to 100 mm, for example, the vibration amplitude is 60 mm, 70 mm, 80 mm, 90 mm or 100 mm; preferably, the vibration amplitude is 100 mm. The vibration frequency is 200 to 500 times / minute, for example, the vibration frequency is 200 times / minute, 300 times / minute, 400 times / minute or 500 times / minute, preferably, the vibration frequency is 500 times / minute. Within this vibration amplitude and vibration frequency range, the screening effect is better.

[0043] Further, during the screening process, the screening residence time is 5 to 15 minutes, for example, the residence time is 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 12.5 minutes or 15 minutes. Within this residence time range, sufficient screening is ensured while reducing screen loss and energy consumption.

[0044] The present invention does not specifically limit the source of the hazardous waste glass slag, including but not limited to the vitreous products formed after high-temperature sintering and melting treatment by resistance furnaces, electric arc furnaces, flame furnaces, fuel furnaces, plasma furnaces, etc.

[0045] In step (2), first, cement and water are mixed to form a cement paste; then, the first particles, the second particles, and some of the third particles are mixed to obtain a first product; finally, the first product is mixed with the cement paste and cured to obtain a concrete product. Among them, the second particles include the second particles M1, the second particles M2, the second particles M3, and the second particles M4.

[0046] The present invention does not limit the way of mixing cement and water, as long as the effect of uniform mixing is achieved. In one embodiment, stirring and mixing are adopted.

[0047] The present invention does not limit the way of mixing the first particles, the second particles, and some of the third particles, as long as the effect of uniform mixing is achieved. In one embodiment, stirring and mixing are adopted.

[0048] The present invention does not limit the way of mixing the first product with the cement paste. In one embodiment, when the first product is mixed with the cement paste, the first product is added to the cement paste and stirred.

[0049] The present invention also does not limit the mixing equipment used. In one embodiment, an automatic mixing blender is used for mixing, such as a concrete mixer.

[0050] The present invention does not further limit the stirring conditions during the preparation of the first product, and it only needs to be mixed evenly.

[0051] In one embodiment, the stirring speed during the preparation of the first product is 100 - 200 r / min. For example, the stirring speed is 100 r / min, 120 r / min, 140 r / min, 160 r / min, 180 r / min or 200 r / min; preferably, the stirring speed is 100 r / min. The stirring time is 3 - 10 min. For example, the stirring time is 3 min, 4 min, 6 min, 8 min or 10 min; preferably, the stirring time is 10 min. Within this stirring speed range and time range, the first particles, M1, M2, M3, M4, and the third particles can be better mixed evenly.

[0052] The present invention does not further limit the stirring speed when the first product is mixed with the cement paste, and it only needs to be mixed evenly.

[0053] Furthermore, the curing method specifically includes: transferring the mixture of the first product and the cement paste to a mold for filling and vibrating tightly, and then placing it in a constant temperature and humidity curing box for curing. The curing temperature is: 20 - 25 °C. For example, the curing temperature is 20 °C, 21 °C, 22 °C, 23 °C, 24 °C or 25 °C; preferably, the curing temperature is 20 °C; the curing humidity is: ≥95%. For example, the curing humidity is 95%, 96%, 97%, 98% or 99%; preferably, the curing humidity is 95%. After curing is completed, demolding is carried out, and the demolded block is placed in a constant temperature and humidity curing box for continued curing, and then high-strength concrete can be obtained.

[0054] It should be noted that when transferring to the mold, the methods of filling, vibrating, and curing in the constant temperature and humidity box can be referred to the "Testing Method for Cement Mortar Strength".

[0055] The present invention does not specifically limit the type of cement, including but not limited to portland cement, ordinary portland cement, slag portland cement, pozzolanic portland cement, fly ash portland cement, etc.

[0056] The present invention does not specifically limit the source of the cement, and commercially available products or products prepared by conventional preparation methods well-known to those skilled in the art can be used.

[0057] In step (3), first, the remaining third particles and the fourth particles obtained in step (1) are mixed evenly to obtain a second product; then, after mixing the second product with fly ash, an alkaline activator is added and mixed evenly, and a geopolymer is obtained after curing.

[0058] The present invention does not limit the mixing method of the second product, and common methods in the art can be used for mixing. It is only necessary to evenly mix the fourth particles and the remaining third particles. For example, mixing can be carried out by stirring.

[0059] The present invention also does not limit the mixing equipment used. In one embodiment, an automatic mixing blender is used for mixing, such as a concrete mixer.

[0060] The present invention does not further limit the stirring conditions during the mixing process, such as the stirring speed and stirring time, as long as the mixing is uniform.

[0061] Further, in order to better prepare the geopolymer, the fly ash used in the present invention is powder collected from the combustion of a circulating fluidized bed boiler, including class I fly ash, class II fly ash, and class III fly ash.

[0062] The present invention does not limit the curing equipment used, and conventional curing equipment in the art can be used. In one embodiment, a common oven or other box with a temperature adjustment function is used; preferably, a common oven is used.

[0063] Further, the curing temperature in step (3) is set to 40 - 60 °C, for example, the curing temperature is 40 °C, 45 °C, 50 °C, 55 °C, or 60 °C; preferably, the curing temperature is 50 °C. According to different temperatures, the curing time is 12 - 24 h, for example, the curing time is 12 h, 16 h, 20 h, or 24 h; preferably, the curing time is 20 h. Within this temperature range, the reaction rate will not be too slow due to too low a temperature, nor will the reaction be too fast due to too high a temperature, resulting in cracking of the concrete block, and at the same time, energy will not be wasted.

[0064] The present invention screens the hazardous waste glass slag into particles with different particle size ranges by means of classification screening, combines the first particles, the second particles, and part of the third particles to form an optimized particle gradation, and manufactures concrete products; since the prepared concrete products do not contain the fourth particles, the subsequent continuous reaction of the fourth particles is avoided, and the compressive strength of the concrete is reduced. At the same time, the alkali reaction characteristics of the fourth particles are fully utilized, and a high-strength geopolymer is produced through a geopolymer reaction using the fourth particles and the remaining third particles as raw materials; since the raw materials do not contain the first particles and the second particles, the reaction efficiency is not too low due to too coarse particles, resulting in poor compressive strength of the prepared geopolymer.

[0065] In a specific embodiment, in step (2), the mass ratio of the first product, cement, and water is 3:1:0.4 to 0.6. Specifically, the mass ratio can be 3:1:0.4, 3:1:0.5, or 3:1:0.6. Preferably, the mass ratio is 3:1:0.5. Within this ratio range, the first product and the cement paste exhibit good fluidity, and the prepared concrete has better compressive strength.

[0066] In a specific embodiment, in step (2), the mass ratio of the first particles, M1, M2, M3, M4, and the third particles in the first product is 0 to 10:10 to 15:10 to 25:20 to 31:20 to 30:5 to 15. For example, the mass ratio of the first particles, M1, M2, M3, M4, and the third particles in the first product is 0:10:10:20:20:5, 5:13:15:25:25:10, or 10:15:25:31:30:15.

[0067] That is to say, the mass percentage of the first particles in the first product can be 0%, 2%, 4%, 6%, 8%, or 10%, or the range composed of any two of these values. The mass percentage of M1 in the first product can be 10%, 11%, 12%, 13%, 14%, or 15%, or the range composed of any two of these values. The mass percentage of M2 in the first product can be 10%, 15%, 20%, or 25%, or the range composed of any two of these values. The mass percentage of M3 in the first product can be 20%, 21%, 22%, 23%, 25%, 27%, 29%, or 31%, or the range composed of any two of these values. The mass percentage of M4 in the first product can be 20%, 22%, 24%, 26%, 28%, or 30%, or the range composed of any two of these values. The mass percentage of the third particles in the first product can be 5%, 7%, 9%, 11%, 13%, or 15%, or the range composed of any two of these values.

[0068] In a specific embodiment, in step (2), during the mixing process of cement and water, the stirring speed is 138 to 142 r / min. Within this stirring speed and stirring time range, the cement and water are mixed more evenly.

[0069] For example, during the mixing process of cement and water, the stirring speed is 138 r / min, 139 r / min, 140 r / min, 141 r / min, or 142 r / min; preferably, the stirring speed is 140 r / min. The stirring time is 0.5 to 0.7 min, for example, 0.5 min, 0.6 min, or 0.7 min, and preferably, the stirring time is 0.5 min.

[0070] In a specific embodiment, in step (2), during the mixing process of the first product and the cement paste, the stirring speed is 275 - 295 r / min, for example, it can be 275 r / min, 280 r / min, 285 r / min, 290 r / min or 295 r / min, and the stirring time is 2 - 4 min, for example, 2 min, 3 min or 4 min. Preferably, the stirring time is 2 min.

[0071] Within this range of stirring speed and stirring time, the first product and the cement paste are mixed more evenly.

[0072] In a specific embodiment, in step (3), the alkaline activator includes a mixture of sodium hydroxide solution and water glass.

[0073] In a specific embodiment, in the mixture, the concentration of the sodium hydroxide solution is 3 - 7.5 mol / L; the mass ratio of the sodium hydroxide solution to water glass is (0.4 - 0.8):1. For example, the concentration of the sodium hydroxide solution is 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L, 5 mol / L, 5.5 mol / L, 6 mol / L, 6.5 mol / L, 7 mol / L or 7.5 mol / L; preferably, the concentration of the sodium hydroxide solution is 5 mol / L. At a specific concentration of the sodium hydroxide solution, the mass ratio of the sodium hydroxide solution to water glass is (0.4 - 0.8):1; for example, the mass ratio is 0.4:1, 0.5:1, 0.6:1, 0.7:1 or 0.8:1; preferably, the mass ratio is 0.6:1. The inventors found that within this specific range, the compressive strength of the geopolymer is higher.

[0074] In a specific embodiment, in step (3), the mass ratio of the second product to fly ash is (2 - 3):1; for example, the mass ratio is 2:1, 2.5:1 or 3:1; preferably, the mass ratio is 2:1. This ratio is set according to the silicon-aluminum ratio and the silicon-sodium ratio. Although the theoretical silicon-aluminum ratio is 1:1, it is possible that not all of the fly ash participates in the reaction. After a large number of experiments, the inventors found that the compressive strength of the geopolymer prepared at this ratio is higher.

[0075] In a specific embodiment, in step (3), the total mass of the second product and fly ash, and the alkaline activator are in a ratio of 1 g:(0.5 - 0.9) mL. For example, the ratio is 1 g:0.5 mL, 1 g:0.6 mL, 1 g:0.7 mL, 1 g:0.8 mL or 1 g:0.9 mL; preferably, the ratio is 1 g:0.5 mL. This ratio is the solid-liquid ratio, and within this solid-liquid ratio range, the second product, fly ash and alkaline activator are mixed more evenly.

[0076] In the present invention, the concentration of sodium hydroxide is affected by the water content, the ratio of sodium hydroxide to water glass affects the activity of the alkali activator, the ratio of the second product to fly ash is as described above, and the solid-liquid ratio affects the reaction performance of the alkali activator and the second product and fly ash and the fluidity of the mixed slurry. Therefore, the setting of the mass ratio of sodium hydroxide to water glass, the mass ratio of ultrafine particles to fly ash, and the solid-liquid ratio are mutually restricted and mutually influential.

[0077] In a specific embodiment, in step (3), in the second product, the mass ratio of the third particles to the fourth particles is 0 to 30:70 to 100. For example, the mass ratio of the third particles to the fourth particles is 0:100, 10:90, 20:80 or 30:70; preferably, the mass ratio of the third particles to the fourth particles is 0:100. Within this ratio range, the compressive strength of the geopolymer is greater.

[0078] In a specific embodiment, in step (3), when the second product and fly ash are stirred and mixed, the stirring speed is 80 to 120 r / min. For example, the stirring speed is 80 r / min, 90 r / min, 100 r / min, 110 r / min or 120 r / min; preferably, the stirring speed is 100 r / min. Further, when the second product and fly ash are stirred and mixed, the stirring time is 5 to 10 min, specifically, it can be 5 min, 6 min, 7 min, 8 min, 9 min or 10 min. Within this stirring speed and time range, the second product and fly ash can be mixed more evenly.

[0079] In a specific embodiment, in step (3), the stirring speed after adding the alkaline activator is 138 to 142 r / min. For example, the stirring speed is 138 r / min, 139 r / min, 140 r / min, 141 r / min or 142 r / min; preferably, the stirring speed is 140 r / min. Further, the stirring time after adding the alkaline activator is 0.5 to 1 min, for example, the stirring time is 0.5 min, 0.6 min, 0.7 min, 0.8 min, 0.9 min or 1 min; preferably, the stirring time is 0.5 min. Within this stirring speed and time range, the second product, fly ash and alkaline activator can be mixed more evenly.

[0080] Hereinafter, the present invention will be further introduced through specific examples.

[0081] In the embodiments of the present invention, the physical and chemical properties of the hazardous waste molten glass slag are shown in Table 1, and the particle size distribution is shown in Table 2:

[0082] Table 1 Chemical composition of hazardous waste glass slag

[0083] Composition Si Ca Fe O Al Ba Ti Na W Proportion 20.42 15.77 13.75 13.49 10.51 10.18 4.38 1.86 1.6

[0084] Table 2 Particle Size Distribution of Hazardous Waste Glass Slag

[0085]

[0086] Example 1

[0087] A method for resource utilization of hazardous waste glass slag, the specific steps are as follows:

[0088] (1) Screening: The hazardous waste glass slag is roughly screened by a vibrating screen. After screening, the hazardous waste glass slag includes first particles, second particles M1, second particles M2, and particles with a size less than 1.18 mm according to particle size. The particle size D1 of the first particles satisfies: D1 ≥ 4.75 mm; the particle size of the second particles M1 satisfies: 2.36 mm ≤ M1 < 4.75 mm; the particle size of the second particles M2 satisfies: 1.18 mm ≤ M2 < 2.36 mm.

[0089] Among them, the first particles, the second particles M1, and the second particles M2 are all coarse particles. The amplitude of the vibrating screen is 1 mm, the vibration frequency is 750 times / min, and the screening residence time is 10 min.

[0090] The particles with a size less than 1.18 mm after screening are further screened by a fine screen into second particles M3, second particles M4, third particles, and fourth particles; the particle size of the second particles M3 satisfies: 0.6 mm ≤ M3 < 1.18 mm; the particle size of the second particles M4 satisfies: 0.3 mm ≤ M4 < 0.6 mm; the particle size D3 of the third particles satisfies: 0.15 mm ≤ D3 < 0.3 mm; the particle size D4 of the fourth particles satisfies: D4 < 0.15 mm.

[0091] Among them, the second particles M3 and the second particles M4 are fine particles; the third particles and the fourth particles are ultra-fine particles. The vibration amplitude of the fine screen is 80 mm, the vibration frequency is 250 times / min, and the screening time is 5 min.

[0092] (2) Preparing concrete products: Using an intelligent weighing device to weigh the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and the third particles, and placing them in an automatic mixing and stirring machine for stirring to obtain a first product. The stirring speed is 100 r / min, and the stirring time is 10 min. Among them, the mass percentages of the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and the third particles in the first product are 5:15:15:30:25:10.

[0093] Weigh cement and water according to a mass ratio of 1:0.5 and stir them. The stirring speed is 140 r / min, and the stirring time is 0.5 min to form a cement paste.

[0094] The first product and cement paste are mixed in a mass ratio of 3:1.5 and stirred thoroughly at a stirring speed of 285 r / min for 2 min. After stirring, the mixture of the first product and cement paste is transferred to a mold for filling and shaking, and then placed in a constant temperature and humidity curing box for curing; after curing is completed, demoulding is performed, and the demoulded block is placed in a constant temperature and humidity curing box for further curing to obtain a concrete product P1.

[0095] (3) Preparation of geopolymer: The third particle and the fourth particle are weighed by an intelligent weighing device, and mixed in an automatic mixer to obtain a second product. The mass ratio of the third particle to the fourth particle is 0:100.

[0096] Fly ash was added according to the mass ratio of the second product to fly ash of 2:1 and stirred until uniform. The stirring speed was 100 r / min and the stirring time was 5 min to obtain a solid material.

[0097] A sodium hydroxide solution with a concentration of 6 mol / L is prepared, and according to a mass ratio of the sodium hydroxide solution to water glass of 0.6:1, water glass is added and mixed thoroughly to obtain an alkaline activator, i.e., a liquid material.

[0098] According to the liquid / solid ratio of 0.5mL:1g, the liquid material and the solid material are mixed and fully stirred at a stirring speed of 140r / min and a stirring time of 0.5min to obtain the stirred slurry. The stirred slurry is transferred to a mold for filling and shaking, and then placed in a constant temperature curing box for curing. The curing box temperature is set to 50°C and the curing time is 20h to obtain geopolymer P2.

[0099] Example 2

[0100] During the coarse screening in step (1), the vibration amplitude of the screening machine is adjusted to 3 mm, the vibration frequency is adjusted to 1000 times / min, and the screening time is 5 min. The other steps are the same as those in Example 1.

[0101] Example 3

[0102] During the fine screening in step (1), the vibration amplitude of the screening machine is adjusted to 60 mm, the vibration frequency is adjusted to 500 times / min, and the screening time is 15 min. The other steps are the same as those in Example 1.

[0103] Example 4

[0104] During the fine screening in step (1), the vibration amplitude of the screening machine is adjusted to 100 mm, the vibration frequency is adjusted to 200 times / min, and the screening time is 5 min. The other steps are the same as those in Example 1.

[0105] Example 5

[0106] Adjust the mass ratio of each raw material in the first product of step (2). Among them, the mass ratio of the first particle, the second particle M1, the second particle M2, the second particle M3, the second particle M4, and the third particle is 0:10:25:30:25:10. Other steps are the same as those in Example 1.

[0107] Example 6

[0108] Adjust the mass ratio of each raw material in the first product of step (2). Among them, the mass ratio of the first particle, the second particle M1, the second particle M2, the second particle M3, the second particle M4, and the third particle is 10:15:20:31:19:5. Other steps are the same as those in Example 1.

[0109] Example 7

[0110] Adjust the mass ratio of each raw material in the first product of step (2). Among them, the mass ratio of the first particle, the second particle M1, the second particle M2, the second particle M3, the second particle M4, and the third particle is 5:10:19:31:20:15. Other steps are the same as those in Example 1.

[0111] Example 8

[0112] Adjust the mass ratio of each raw material in the first product of step (2). Among them, the mass ratio of the first particle, the second particle M1, the second particle M2, the second particle M3, the second particle M4, and the third particle is 10:15:25:30:15:5. Other steps are the same as those in Example 1.

[0113] Example 9

[0114] Adjust the mass ratio of each raw material in the second product of step (3). Among them, the mass ratio of the third particle and the fourth particle is 10:90. Other steps are the same as those in Example 1.

[0115] Example 10

[0116] Adjust the mass ratio of each raw material in the second product of step (3). Among them, the mass ratio of the third particle and the fourth particle is 20:80. Other steps are the same as those in Example 1.

[0117] Example 11

[0118] Adjust the mass ratio of each raw material in the second product of step (3). Among them, the mass ratio of the third particle and the fourth particle is 30:70. Other steps are the same as those in Example 1.

[0119] Example 12

[0120] Adjust the mass ratio of each raw material in the second product of step (3), where the mass ratio of the third particles to the fourth particles is 40:60. Other steps are the same as those in Example 1.

[0121] Example 13

[0122] Adjust the mass ratio of the second product to fly ash in step (3) to 1:1. Other steps are the same as those in Example 1.

[0123] Example 14

[0124] Adjust the mass ratio of the second product to fly ash in step (3) to 2.5:1. Other steps are the same as those in Example 1.

[0125] Example 15

[0126] Adjust the mass ratio of the second product to fly ash in step (3) to 3:1. Other steps are the same as those in Example 1.

[0127] Example 16

[0128] Adjust the mass ratio of the second product to fly ash in step (3) to 4:1. Other steps are the same as those in Example 1.

[0129] Example 17

[0130] Adjust the concentration of the sodium hydroxide solution in step (3) to 3 mol / L. Other steps are the same as those in Example 1.

[0131] Example 18

[0132] Adjust the concentration of the sodium hydroxide solution in step (3) to 7.5 mol / L. Other steps are the same as those in Example 1.

[0133] Example 19

[0134] In the sodium hydroxide solution in step (3), adjust the mass ratio of NaOH (solute) / sodium silicate to 0.4. Other steps are the same as those in Example 1.

[0135] Example 20

[0136] In step (4), adjust the ratio of NaOH (solute) / sodium silicate to 0.55. Other steps are the same as those in Example 10.

[0137] Example 21

[0138] In step (4), adjust the ratio of NaOH (solute) / sodium silicate to 0.56. Other steps are the same as those in Example 10.

[0139] Example 22

[0140] Adjust the mass ratio of NaOH (solute) to sodium silicate in step (3) to 0.8, and keep other steps the same as in Example 1.

[0141] Example 23

[0142] Adjust the liquid-solid ratio in step (3) to 0.6, that is, the ratio of the total mass of the second product and fly ash to the alkaline activator is 1 g: 0.6 mL, and keep other steps the same as in Example 1.

[0143] Example 24

[0144] Adjust the liquid-solid ratio in step (3) to 0.7, that is, the ratio of the total mass of the second product and fly ash to the alkaline activator is 1 g: 0.7 mL, and keep other steps the same as in Example 1.

[0145] Example 25

[0146] Adjust the liquid-solid ratio in step (3) to 0.8, that is, the ratio of the total mass of the second product and fly ash to the alkaline activator is 1 g: 0.8 mL, and keep other steps the same as in Example 1.

[0147] Example 26

[0148] Adjust the liquid-solid ratio in step (3) to 0.9, that is, the ratio of the total mass of the second product and fly ash to the alkaline activator is 1 g: 0.9 mL, and keep other steps the same as in Example 1.

[0149] Example 27

[0150] Adjust the stirring speed of the second product and fly ash in step (3) to 80 r / min, and the stirring time is 1 min, and keep other steps the same as in Example 1.

[0151] Example 28

[0152] Adjust the stirring speed of the second product and fly ash in step (3) to 120 r / min, and the stirring time is 0.5 min, and keep other steps the same as in Example 1.

[0153] Example 29

[0154] Adjust the curing temperature in step (3) to 40 °C, and the curing time is 24 h.

[0155] Example 30

[0156] Adjust the curing temperature in step (3) to 60 °C, and the curing time is 12 h.

[0157] Comparative Example 1

[0158] Adjust the mass ratio in the first product of step (2), where the mass ratio of the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and some of the third particles is 100:0:0:0:0:0, that is, all the first particles are used to prepare the concrete product. Other steps are the same as those in Example 1.

[0159] Comparative Example 2

[0160] Adjust the mass ratio in the first product of step (2), where the mass ratio of the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and some of the third particles is 0:100:0:0:0:0, that is, all the second particles M1 are used to prepare the concrete product. Other steps are the same as those in Example 1.

[0161] Comparative Example 3

[0162] Adjust the mass ratio in the first product of step (2), where the mass ratio of the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and some of the third particles is 0:0:100:0:0:0, that is, all the second particles M2 are used to prepare the concrete product. Other steps are the same as those in Example 1.

[0163] Comparative Example 4

[0164] Adjust the mass ratio in the first product of step (2), where the mass ratio of the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and some of the third particles is 0:0:0:100:0:0, that is, all the second particles M3 are used to prepare the concrete product. Other steps are the same as those in Example 1.

[0165] Comparative Example 5

[0166] Adjust the mass ratio in the first product of step (2), where the mass ratio of the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and some of the third particles is 0:0:0:0:100:0, that is, all the second particles M4 are used to prepare the concrete product. Other steps are the same as those in Example 1.

[0167] Comparative Example 6

[0168] Adjust the mass ratio in the first product of step (2), where the mass ratio of the first particles, the second particles M1, the second particles M2, the second particles M3, the second particles M4, and some of the third particles is 0:0:0:0:0:100, that is, all the third particles are used to prepare the concrete product. Other steps are the same as those in Example 1.

[0169] Table 3 Compressive Strengths of Concrete Products and Geopolymers Prepared in Different Groups

[0170]

[0171]

[0172] As can be seen from Table 3, compared with the comparative examples, the compressive strengths of the concrete products and geopolymers prepared in the examples are both higher. The highest compressive strength of the concrete products can reach 36.2 MPa, and the highest compressive strength of the geopolymers can reach 46.23 MPa. It shows that the method for resource utilization of hazardous waste glass slag provided by the present invention can simultaneously improve the compressive strengths of the prepared concrete products and geopolymers.

[0173] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for resource utilization of hazardous waste glass slag, characterized in that: The steps include: (1) Screening: Screening the hazardous waste glass slag according to particle size to obtain first particles, second particles, third particles and fourth particles; the particle size D1 of the first particles satisfies: D1 ≥ 4.75 mm; the particle size D2 of the second particles satisfies: 0.3 mm ≤ D2 < 4.75 mm; the second particles include second particles M1, second particles M2, second particles M3 and second particles M4; the particle size of the second particles M1 satisfies: 2.36 mm ≤ M1 < 4.75 mm; the particle size of the second particles M2 satisfies: 1.18 mm ≤ M2 < 2.36 mm; the particle size of the second particles M3 satisfies: 0.6 mm ≤ M3 < 1.18 mm; the particle size of the second particles M4 satisfies: 0.3 mm ≤ M4 < 0.6 mm; the particle size D3 of the third particles satisfies: 0.15 mm ≤ D3 < 0.3 mm; the particle size D4 of the fourth particles satisfies: D4 < 0.15 mm; (2) preparing a concrete product: mixing cement and water to obtain a cement paste; mixing the first particles, the second particles, and a portion of the third particles to obtain a first product; mixing the first product with the cement paste and then curing to obtain a concrete product; (3) Preparing geopolymer: mixing the remaining third particles and the fourth particles to obtain a second product, mixing the second product with fly ash, adding an alkaline activator and mixing evenly; and curing to obtain a geopolymer.

2. The method according to claim 1, characterized in that In step (2), the mass ratio of the first product, cement and water is 3:1:0.4-0.

6.

3. The method according to claim 1 or 2, characterized in that: In step (2), the mass ratio of the first particles, M1, M2, M3, M4, and the third particles in the first product is 0-10:10-15:10-25:20-31:20-30:5-15.

4. The method according to any one of claims 1 to 3, characterized in that: In step (2), during the mixing process of the cement and water, the stirring speed is 138-142 r / min; And / or, during the mixing process of the first product and the cement slurry, the stirring speed is 275-295 r / min.

5. The method according to any one of claims 1 to 4, characterized in that: In step (3), the alkaline activator comprises a mixture of sodium hydroxide solution and water glass.

6. The method according to claim 5, characterized in that In the mixed solution, the concentration of the sodium hydroxide solution is 3-7.5 mol / L, and the mass ratio of the sodium hydroxide solution to water glass is (0.4-0.8):

1.

7. The method according to any one of claims 1 to 6, characterized in that: In step (3), the mass ratio of the second product to the fly ash is (2-3):

1.

8. The method according to any one of claims 1 to 7, characterized in that: In step (3), the ratio of the total mass of the second product and the fly ash to the alkaline activator is 1 g: (0.5-0.9) mL.

9. The method according to any one of claims 1 to 8, characterized in that: In step (3), in the second product, the mass ratio of the third particles to the fourth particles is 0-30:70-100.

10. The method according to any one of claims 1 to 9, characterized in that: In step (3), during the mixing of the second product and the fly ash, the stirring speed is 80 to 120 r / min; And / or, during the mixing process after adding the alkaline activator, the stirring speed is 138-142 r / min.

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