CN115108743A - Method for preparing carbonized foam geopolymer by using garbage incinerator bottom slag and garbage incineration fly ash and application of carbonized foam geopolymer - Google Patents
Method for preparing carbonized foam geopolymer by using garbage incinerator bottom slag and garbage incineration fly ash and application of carbonized foam geopolymer Download PDFInfo
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Abstract
The invention belongs to the field of comprehensive utilization of solid waste resources, and discloses a method for preparing a carbonized foam geopolymer by using bottom slag of a garbage incinerator and garbage incineration fly ash and application thereof. The method incinerates the garbageThe fly ash is compounded with a melting assistant, the glass slag is obtained after high-temperature melting, the obtained glass slag is compounded with garbage incinerator bottom slag, the glass slag is pretreated and then mixed with a foaming agent, an alkali activator and a foam stabilizer, activation reaction and foaming reaction are carried out under the action of the alkali activator and the foaming agent, and the carbonized foam geopolymer is obtained after molding, maintenance, demolding and carbonization. The invention realizes 'treating waste with waste and changing waste into valuable', and simultaneously catches and utilizes CO 2 To make CO 2 The method has the advantages of permanent sealing, multiple meanings of recycling, energy conservation and emission reduction, simple process, low cost, strong operability and high additional value when being used for preparing the foam material, and solves the problem of green and cooperative recycling of the bottom slag of the garbage incinerator and the fly ash of the garbage incineration.
Description
Technical Field
The invention relates to the field of comprehensive utilization of solid waste resources, in particular to a method for preparing a carbonized foam geopolymer by using bottom slag of a garbage incinerator and fly ash of the garbage incinerator and application thereof.
Background
The household garbage incineration generates a large amount of incineration residue solid waste, including garbage incinerator bottom slag and garbage incineration fly ash. The incinerator bottom slag is a heterogeneous mixture of silicates, metals, oxidized polymers, unburned organics and other non-combustible materials, produced in amounts of about 80-90% of the total waste residue after incineration. The bottom slag of the garbage incinerator belongs to general solid waste, but the inside of the bottom slag also contains harmful heavy metals such as Cr, Pb, Zn, Cu and the like. The waste incineration fly ash is mainly generated in the flue gas purification process of the incinerator and is concentrated in a flue gas pipeline, a dust removal device and a purification device, and the generated amount accounts for 2-5% of the total amount of the primary waste. The waste incineration fly ash contains quite complex components, including heavy metal salts, sulfides, nitrates/nitrites, activated carbon, dioxin and the like, wherein the heavy metals and the dioxin are serious in environmental hazard. The heavy metal species in the waste incineration fly ash mainly comprise Cd, Cr, Cu, Ni, Pb, Hg and the like. According to the national hazardous waste catalogue (2021 edition), the fly ash from incineration of garbage still belongs to hazardous waste of HW18 category. In 2020, the yield of the waste incineration fly ash in China exceeds 1000 million tons, the disposal by a landfill method and the cement solidification disposal have the risk of environmental pollution, and the melting solidification method is gradually emphasized. GB/T41015-2021 technical requirement for vitrification treatment products of solid wastes comes out in 2021, and the waste incineration fly ash plasma molten glass body can be used as building materials to meet the technical requirement for vitrification treatment products of solid wastes, so that a new way is found for the products of the high-temperature melting technology of the waste incineration fly ash.
With the development of science and technology, novel building materials are also developing and changing, the foam material has the excellent characteristics of light weight, high strength, heat preservation, energy conservation, decoration and the like, and has some defects, such as low strength, insufficiently firm combination of matrix, high cost and the like. The carbonization technology not only enhances the mechanical property of the material, but also can treat CO 2 The capture and utilization of the organic matter are also of great significance. The method for preparing the carbonized foam geopolymer by using the waste incinerator bottom slag and the waste incineration fly ash is an effective means of resource utilization, high-valued, low-carbon and environmental protection, and simultaneously the cost of the foam material is obviously reduced.
Chinese patent CN113307554A discloses a method for preparing foamed geopolymer from waste incineration ash. And ball-milling the garbage incinerator bottom slag and fly ash, mixing with an alkaline activator, stirring, pouring, maintaining and demolding to obtain the porous geopolymer. According to the invention, waste incineration fly ash and waste incinerator bottom slag are subjected to ball milling pretreatment and then directly mixed with an activator to react to obtain a geopolymer, the waste incineration fly ash is not subjected to pretreatment, dioxin, heavy metals and chloride in the fly ash have potential risks to the environment and product quality, and aluminum in the waste incinerator bottom slag is used as a foaming agent for foaming, so that the foaming process is not easy to control, and bubbles are difficult to capture, so that the foaming is not uniform, and the problem of poor operability exists.
The harmless disposal of the waste incineration fly ash and the waste incineration furnace bottom slag has the problems of low efficiency, high cost, high energy consumption, long process flow, poor operability and the like. Therefore, the development of a harmless and high-valued treatment method with environmental protection, strong operability and high added value is urgently needed.
Disclosure of Invention
Aiming at the problems of the prior art, the invention provides a method for preparing carbonized foam geopolymer by using garbage incinerator bottom slag and garbage incineration fly ash and application thereof, which not only solves the problems of low treatment efficiency, high cost, high energy consumption, long process flow, poor operability and the like of the garbage incinerator bottom slag and the garbage incineration fly ash, realizes 'treatment of waste by waste and waste change into valuable', but also traps and utilizes CO 2 The method has multiple meanings of recycling, energy conservation and emission reduction, is used for preparing the foam material, and has the advantages of simple process, low cost, strong operability and high added value.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a method for preparing carbonized foam geopolymer by cooperating bottom slag of a garbage incinerator with fly ash of garbage incineration comprises the steps of compounding the fly ash of garbage incineration with a melting auxiliary agent, and obtaining glass slag after high-temperature melting; pretreating the obtained glass slag compounded with the bottom slag of the garbage incinerator, mixing the pretreated glass slag with a foaming agent, an alkali activator and a foam stabilizer, performing activation reaction and foaming reaction under the action of the alkali activator and the foaming agent, and finally performing forming, maintenance, demolding and carbonization to obtain a carbonized foam geopolymer; wherein, the flue gas generated in the melting process is rapidly reduced to below 200 ℃ through a flue gas quenching device, so that the residual chloride is prevented from synthesizing dioxin again.
The method for preparing the carbonized foam geopolymer by using the waste incinerator bottom slag and the waste incineration fly ash comprises the following steps:
step 1, compounding and mixing 30-80 wt.% of waste incineration fly ash and 20-70 wt.% of melting auxiliary agent, wherein the total amount is 100 wt.%;
step 2, carrying out high-temperature melting on the uniformly mixed waste incineration fly ash and the melting auxiliary agent, and carrying out air quenching to obtain glass slag; wherein, the flue gas generated in the melting process is rapidly reduced to below 200 ℃ through a flue gas quenching device, so that the residual chloride is prevented from synthesizing dioxin again;
step 3, mixing 20-80 wt.% of glass slag and 20-80 wt.% of garbage incinerator bottom slag to obtain a compound material, wherein the total amount is 100 wt.%;
step 4, pretreating the compound material to obtain a mixture, wherein the pretreatment comprises dry grinding and screening;
step 5, mixing the mixture with a foaming agent, a foam stabilizer and an alkali activator;
step 6, injecting the mixed slurry into a mold for an activation reaction and a foaming reaction, sealing after the reaction is carried out for 10-60 min to obtain a molded blank, and curing for 0.5-48 h in a curing box with the temperature of 20-100 ℃ and the relative humidity of 60-98% RH;
step 7, demolding the molded blank obtained after curing, and then carrying out CO carbonization at the temperature of 20-100 DEG C 2 And carbonizing for 0.5-3 h in a carbonization box with the concentration of 20-80% to obtain the carbonized foam geopolymer.
The improvement is that the melting auxiliary agent in the step 1 is one or a mixture of a plurality of waste glass, quartz sand, borax or waste incineration bottom ash.
The improvement is that the temperature of the high-temperature melting in the step 2 is 1100-1800 ℃, and the heat preservation time is 5-120 min.
The improvement is that the mixture obtained by dry grinding and screening in the step 4 comprises the following specific steps: (1) dry grinding: dry grinding is carried out for 15-120 min, and the ball material ratio is 1: 1-3: 1; (2) screening: and screening the glass slag after dry grinding by using a sieve with the aperture less than or equal to 2mm to remove coarse materials, thus obtaining a mixture.
The improvement is that the alkaline activator added in the step 5 is a mixture of sodium hydroxide and water glass, the weight ratio of the sodium hydroxide to the water glass is 1: 3-6: 1, and the addition amount of the alkaline activator is 10-20 wt% of the mixture; the foaming agent is hydrogen peroxide, and the addition amount of the foaming agent is 1-10 wt.% of the mixture; the foam stabilizer is a mixture of sodium dodecyl benzene sulfonate and triethanolamine, the weight ratio of the sodium dodecyl benzene sulfonate to the triethanolamine is 1:1, and the adding amount of the foam stabilizer is 1-8 wt% of the mixture.
A carbonized foamed geopolymer prepared by any of the above methods.
The carbonized foam geopolymer prepared by the method is applied to the preparation of foam heat-insulating materials or foam refractory materials.
The invention principle is as follows:
according to the invention, the glass slag obtained by melting the waste incineration fly ash and the melting auxiliary agent at high temperature is compounded with the waste incineration bottom slag, dioxin is thoroughly decomposed after the fly ash is melted at high temperature, most heavy metals and chlorine salts are volatilized, and residual heavy metals and chlorine salts are solidified in a vitreous body, so that the toxicity of the waste incineration fly ash is obviously reduced. Activating glass melt and garbage incinerator bottom slag and SiO in material by using alkali excitant 2 And Al 2 O 3 Activating with alkali activator to form Al-O ([ AlO ] 4 ] 5- ) Tetrahedron and Si-O tetrahedron ([ SiO ] 4 ] 4- ) Of an amorphous to semicrystalline aluminosilicate polymer of, H 2 O 2 The foaming process of the glass slag under the action of the alkali activator can be roughly divided into 3 stages of bubble nucleus formation, bubble growth, bubble stabilization and solidification, H 2 O 2 The foaming agent is decomposed into water and oxygen under the action of the alkali activator, the foaming effect is obvious, the foaming time is short, the foaming forming is carried out at normal temperature, and the operability is strong and easy to control. MgO, f-CaO and the like in the materials seriously affect the stability of the product, and the MgO, the f-CaO and the like and CO are carbonized 2 Chemical reaction occurs, and the potential risk of late stability of the prepared product is eliminated.
Has the advantages that:
compared with the prior art, the method for preparing the carbonized foam geopolymer by using the garbage incinerator bottom slag and the garbage incineration fly ash and the application thereof have the advantages of simple process, low cost, no pollution, strong operability and easy industrialization, and have the following advantages:
(1) the alkali-activated technology can cause the problems of material durability and environmental risks due to high alkali consumption, and the carbonization technology needs to additionally add cementing components such as cement and lime due to insufficient raw material gelatinization and low carbonization efficiency;
(2) the alkali excitation effect promotes the activity excitation of the bottom slag of the waste incinerator and the molten glass slag of the fly ash of the waste incinerator, and additionally provides reactants capable of generating carbonization, so that the carbonization efficiency is improved, and the performance of carbonized products is optimized; the compactness of the matrix is improved by carbonization, and the performance of the product is improved; the wall material is prepared by utilizing the synergistic action of alkali excitation and carbonization, thereby realizing the resource utilization of the bottom slag of the waste incinerator and the fused glass slag of the fly ash from the waste incineration as well as the CO 2 The method has the advantages of trapping and utilization, and has multiple meanings of resource utilization, energy conservation and emission reduction;
(3) the invention utilizes enough SiO in solid waste 2 And Al 2 O 3 No need of compounding other solid wastes, reduced difficulty of component preparation process, and reduced content of SiO 2 And Al 2 O 3 Carrying out activation reaction with an alkali activator to form Al-O ([ AlO ] 4 ] 5- ) Tetrahedron and Si-O tetrahedron ([ SiO ] 4 ] 4- ) Amorphous to semi-crystalline aluminosilicate polymers of (a); h 2 O 2 The foaming process of the glass slag under the action of the alkali-activator can be roughly divided into 3 stages of bubble nucleus formation, bubble growth, bubble stabilization and solidification, H 2 O 2 The foaming agent is decomposed into water and oxygen under the action of the alkali activator, the foaming effect is obvious, the foaming time is short, the foaming forming is carried out at normal temperature, and the operability is strong;
(4) free MgO, CaO and the like seriously affect the stability of the product, and the carbonized MgO, CaO and the like and CO 2 The chemical reaction is carried out to generate a carbonate mineral phase, thereby not only eliminating the potential risk of the later stability of the product,also captures and utilizes CO 2 ;
(5) Dioxin in the waste incineration fly ash is decomposed into small molecular chloride after plasma high-temperature melting, and is rapidly cooled to below 200 ℃ through a flue gas quenching device, so that the dioxin is prevented from being synthesized again;
(6) the thermal conductivity coefficient (25 ℃) of the carbonized foam geopolymer prepared by the invention is 0.20-0.45W/(m.K); the density is 410-700kg/m 3 (ii) a The average strength is 7.5-15.0MPa, the fire-proof grade is A grade, and the material has excellent performances of heat insulation, fire prevention, sound absorption, moisture prevention, light weight, high strength and the like, and is a novel environment-friendly material.
Drawings
FIG. 1 is a schematic process flow diagram of a method for preparing carbonized foam geopolymer by using bottom slag of a garbage incinerator and fly ash of the garbage incinerator in cooperation with the carbonized foam geopolymer in the embodiment of the invention.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Carbonizing: by carbonisation is meant CO 2 The final product is mainly calcium carbonate crystal with various crystal forms, and the carbonization is an effective permanent carbon fixation method.
Example 1
30 wt.% waste incineration fly ash and 70wt.% waste glass are mixed and then melted in a high-temperature furnace at 1100 ℃ for 120min, glass slag is obtained by air quenching, and flue gas generated in the melting process is rapidly reduced to below 200 ℃ through a flue gas quenching device. And (2) mixing 20wt.% of glass slag and 80wt.% of garbage incinerator bottom slag, dry-grinding for 15min by using a ball mill, wherein the ball-to-material ratio is 2:1, and screening the dry-ground glass slag by using a sieve with the aperture of 2mm to remove coarse materials to obtain a mixture. Plus 1 wt.% H 2 O 2 10wt.% of alkaline activator and 1 wt.% of foam stabilizer, wherein the alkaline activator is a mixture of sodium hydroxide and water glass in a ratio of 1:2, and the foam stabilizer is a mixture of sodium dodecyl benzene sulfonate and triethanolamine in a ratio of 1: 1. The materials are mixed evenly to obtainInjecting the slurry into a mold for activation reaction and foaming reaction for 10min, sealing in a curing box with a temperature of 20 ℃ and a relative humidity of 98% RH for curing for 24h, demolding to obtain a blank body, and curing at a temperature of 60 ℃ and CO 2 Carbonizing for 3h in a carbonization box with the concentration of 20% to obtain the carbonized foam geopolymer.
The carbonized foam geopolymer prepared in the examples was subjected to performance tests according to the composite insulating brick and composite insulating block (GBT 29060-: the thermal conductivity (25 ℃) is 0.20W/(mK); the density was 410kg/m 3 (ii) a The average strength is 14MPa, and the fire-retardant rating is A.
The preparation of the carbonised foamed geopolymer was carried out according to the preparation method of example 1, with different parameters, as shown in table 1 below.
TABLE 1 different parameter combinations for the preparation process according to the invention
Note: for clarity, the parameters of example 1 are filled into a table.
The carbonized foamed geopolymers prepared under different parameters in table 1 were subjected to performance tests, the test methods were performed with reference to example 1, and the resulting performance data are shown in table 2.
TABLE 2 Properties of the carbonized foam geopolymers prepared under different parameters
Examples | Thermal conductivity (25 ℃ C.) W/(m. K) | Density, kg/m3 | Average compressive strength, MPa | Fire rating |
1 | 0.2 | 410 | 14 | Class A |
2 | 0.38 | 500 | 12 | Class A |
3 | 0.4 | 430 | 10 | Class A |
4 | 0.42 | 445 | 8 | Class A |
5 | 0.44 | 460 | 7.5 | Class A |
6 | 0.28 | 475 | 8.3 | Class A |
7 | 0.3 | 490 | 9.1 | Class A |
8 | 0.34 | 505 | 9.9 | Class A |
9 | 0.36 | 520 | 10.7 | Class A |
10 | 0.38 | 535 | 15 | Class A |
11 | 0.4 | 550 | 12.3 | Class A |
12 | 0.42 | 565 | 13.1 | Class A |
13 | 0.45 | 580 | 13.9 | Class A |
14 | 0.28 | 595 | 14.7 | Class A |
15 | 0.3 | 610 | 9.9 | Class A |
16 | 0.32 | 625 | 10.7 | Class A |
17 | 0.34 | 640 | 11.5 | Class A |
18 | 0.36 | 655 | 12.3 | Class A |
19 | 0.38 | 670 | 8 | Class A |
20 | 0.4 | 685 | 7.5 | Class A |
21 | 0.42 | 700 | 8.3 | Class A |
22 | 0.44 | 490 | 9.1 | Class A |
23 | 0.28 | 505 | 9.9 | Class A |
24 | 0.3 | 520 | 10.7 | Class A |
25 | 0.4 | 535 | 11.5 | Class A |
26 | 0.42 | 550 | 12.3 | Class A |
27 | 0.44 | 565 | 13.1 | Class A |
28 | 0.28 | 580 | 13.9 | Class A |
In conclusion, the invention realizes 'treating waste by waste and changing waste into valuable', and simultaneously captures and utilizes CO 2 To make CO 2 The method has the advantages of permanent sealing, multiple meanings of recycling, energy conservation and emission reduction, simple process, low cost, strong operability and high added value when being used for preparing the foam material, and solves the problem of green recycling cooperative disposal of the bottom slag of the garbage incinerator and the fly ash of the garbage incineration.
Claims (8)
1. A method for preparing carbonized foam geopolymer by using bottom slag of a garbage incinerator and fly ash of the garbage incinerator is characterized in that the fly ash of the garbage incinerator is compounded with a melting auxiliary agent and is melted at high temperature to obtain glass slag; pretreating the obtained glass slag compounded with the bottom slag of the garbage incinerator, mixing the pretreated glass slag with a foaming agent, an alkali activator and a foam stabilizer, performing activation reaction and foaming reaction under the action of the alkali activator and the foaming agent, and finally performing forming, maintenance, demolding and carbonization to obtain a carbonized foam geopolymer; wherein, the flue gas generated in the melting process is rapidly reduced to below 200 ℃ through a flue gas quenching device, so that the residual chloride is prevented from synthesizing dioxin again.
2. The method for preparing the carbonized foam geopolymer by using the bottom slag of the garbage incinerator and the fly ash of the garbage incineration as the raw materials according to claim 1, which is characterized by comprising the following steps:
step 1, mixing 30-80 wt.% of waste incineration fly ash and 20-70 wt.% of melting auxiliary agent, wherein the total amount is 100 wt.%;
step 2, carrying out high-temperature melting on the uniformly mixed waste incineration fly ash and the melting auxiliary agent, and carrying out air quenching to obtain glass slag; wherein, the flue gas generated in the melting process is rapidly reduced to below 200 ℃ through a flue gas quenching device, so that the residual chloride is prevented from synthesizing dioxin again;
step 3, mixing 20-80 wt.% of glass slag and 20-80 wt.% of garbage incinerator bottom slag to obtain a compound material, wherein the total amount is 100 wt.%;
step 4, pretreating the compound material to obtain a mixture, wherein the pretreatment comprises dry grinding and screening;
step 5, mixing the mixture with a foaming agent, a foam stabilizer and an alkali activator to obtain mixed slurry;
step 6, injecting the mixed slurry into a mold for an activation reaction and a foaming reaction, sealing after the reaction is carried out for 10-60 min to obtain a molded blank, and curing for 0.5-48 h in a curing box with the temperature of 20-100 ℃ and the relative humidity of 60-98% RH;
step 7, demolding the cured molded blank, and then carrying out CO carbonization at the temperature of 20-100 DEG C 2 Carbonizing for 0.5-3 h in a carbonization box with the concentration of 20% -80% to obtain the carbonized foam geopolymer.
3. The method for preparing carbonized foam geopolymer by using the bottom slag of the garbage incinerator and the fly ash of the garbage incinerator as claimed in claim 2, wherein the melting auxiliary agent in step 1 is one or more of waste glass, quartz sand, borax or the bottom ash of the garbage incinerator.
4. The method for preparing the carbonized foam geopolymer by using the bottom slag of the garbage incinerator and the fly ash of the garbage incinerator as claimed in claim 2, wherein the temperature of the high-temperature melting in step 2 is 1100-1800 ℃, and the heat preservation time is 5-120 min.
5. The method for preparing the carbonized foam geopolymer by using the bottom slag of the garbage incinerator and the fly ash of the garbage incinerator according to claim 2, wherein the mixture is obtained by dry grinding and screening in step 4, and the method comprises the following specific steps: (1) dry grinding: dry grinding is carried out for 15-120 min, and the ball material ratio is 1: 1-3: 1; (2) screening: and screening the glass slag after dry grinding by using a sieve with the aperture less than or equal to 2mm to remove coarse materials, thus obtaining a mixture.
6. The method for preparing the carbonized foam geopolymer by using the bottom slag of the garbage incinerator and the fly ash of the garbage incineration as the main components according to claim 2, wherein the alkaline activator added in the step 5 is a mixture of sodium hydroxide and water glass, the weight ratio of the sodium hydroxide to the water glass is 1: 3-6: 1, and the addition amount of the alkaline activator is 10-20 wt% of the mixture; the foaming agent is hydrogen peroxide, and the addition amount of the foaming agent is 1-10 wt.% of the mixture; the foam stabilizer is a mixture of sodium dodecyl benzene sulfonate and triethanolamine, the weight ratio of the sodium dodecyl benzene sulfonate to the triethanolamine is 1:1, and the addition amount of the foam stabilizer is 1-8 wt% of the mixture.
7. A carbonized foamed geopolymer prepared according to the process of any one of claims 1 to 6.
8. Use of the carbonized foamed geopolymer obtained according to claim 1 or 7 for the preparation of foamed thermal insulation or foamed refractory.
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CN115710094A (en) * | 2022-12-01 | 2023-02-24 | 光大环境科技(中国)有限公司 | Full-quantitative recycling method for bottom slag of garbage incinerator |
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