CN113372097A - Phase-change ceramsite based on waste incineration fly ash and preparation method and application thereof - Google Patents
Phase-change ceramsite based on waste incineration fly ash and preparation method and application thereof Download PDFInfo
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- CN113372097A CN113372097A CN202110863688.6A CN202110863688A CN113372097A CN 113372097 A CN113372097 A CN 113372097A CN 202110863688 A CN202110863688 A CN 202110863688A CN 113372097 A CN113372097 A CN 113372097A
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/135—Combustion residues, e.g. fly ash, incineration waste
- C04B33/1352—Fuel ashes, e.g. fly ash
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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Abstract
The invention relates to a phase-change ceramsite based on waste incineration fly ash and a preparation method and application thereof. The fly ash ceramsite comprises 15-45 parts of raw material waste incineration fly ash, 25-45 parts of clay and 25-55 parts of municipal sludge by weight, and the phase-change material is loaded in the capillary structure of the fly ash ceramsite. The problem of preparing the phase-change ceramsite by utilizing the waste incineration fly ash is solved, resources are effectively utilized, the waste incineration fly ash can be safely disposed, and high-value utilization of the fly ash ceramsite is realized.
Description
Technical Field
The invention belongs to the technical field of inorganic nonmetallic materials, and particularly relates to phase-change ceramsite based on waste incineration fly ash, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the rapid development of urbanization in China and the increasing improvement of the living standard of people, the yield of municipal domestic waste is rapidly increased. The production of urban domestic garbage is increasing day by day, and the annual growth rate is rapidly increased by 8-10%. The volume of the garbage can be reduced by 90% by burning the garbage, and the chemical energy stored in the garbage can be converted into other forms of energy such as heat energy, and the like, so that the garbage incinerator has the advantages of high treatment speed, small occupied area, high reduction and harmless efficiency, resource recycling and the like. The waste incineration fly ash refers to residue collected in a flue gas purification system of a waste incineration power plant, and the total amount of the waste incineration fly ash is 3% -4% of the treatment amount of domestic waste. The generation amount of fly ash generated by waste incineration in China is huge, and the fly ash is continuously increased in the future along with the explosive growth of the waste incineration industry, the total incineration amount of the waste reaches 59.14 ten thousand tons/day in 2020, the amount of fly ash generated in the year is about 1000 ten thousand tons, and the fly ash resource recycling treatment is imperative. National records of hazardous wastes list solid waste incineration fly ash as the hazardous waste number HW 18-251. The main reason that the toxicity of the fly ash is high is that the waste incineration causes part of heavy metals to volatilize at high temperature and then condense and attach on fly ash particles in a flue gas purification system; in addition, dioxin generated by incineration of garbage also adheres to the fly ash particles. Therefore, the waste incineration fly ash often contains heavy metals such as lead (Pb) and cadmium (Cd) with high leaching concentration and dioxin with high concentration, and is generally subjected to solidification/stabilization treatment before final disposal.
At present, cement solidification, asphalt solidification, melting solidification technology, chemical agent solidification stabilization and the like are taken as measures for safe and harmless treatment of waste incineration fly ash, and products after solidification stabilization treatment, such as meeting leaching toxicity standards or resource utilization standards, can enter a landfill for landfill treatment or resource utilization. The treatment cost of the fly ash treatment mode is generally higher, the large-scale popularization and application difficulty is higher, and most of the incineration fly ash is still subjected to landfill treatment at present. The land for landfill is short, the construction investment is large, and the harmfulness of the dissolution of heavy metals and dioxin to human health and living environment cannot be ignored. Therefore, how to adopt a proper technology to treat the waste incineration fly ash and achieve the aims of stabilization, resource utilization and harmlessness becomes a problem to be solved urgently in society.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a phase-change ceramsite based on waste incineration fly ash, and a preparation method and application thereof. The fly ash is sintered at high temperature through a rotary kiln system, heavy metals in the fly ash are melted and solidified in the ceramsite, and dioxin is pyrolyzed at high temperature, so that the fly ash is treated in a harmless and recycling manner, the fly ash ceramsite is used as a carrier and is loaded with a phase-change material to prepare the phase-change energy storage ceramsite, and the phase-change energy storage ceramsite is effectively utilized as a resource, so that the waste incineration fly ash can be safely treated, and the high-value utilization of the fly ash ceramsite is realized.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the phase-change ceramsite based on waste incineration fly ash comprises 15-45 parts of fly ash, 25-45 parts of clay and 25-55 parts of municipal sludge by weight, wherein the fly ash ceramsite comprises a capillary pore structure, and the phase-change material is loaded in the capillary pore structure of the fly ash ceramsite.
The phase-change ceramsite is prepared from waste incineration fly ash, the phase-change ceramsite comprises a ceramsite material and a phase-change material, the ceramsite material is prepared from incineration fly ash, clay and municipal sludge, wherein the clay mainly comprises SiO2And Al2O3The percentage of the SiO is respectively 50.24 percent and 42.24 percent, and the SiO is needed for sintering the ceramsite2And Al2O3The components improve the molding rate and the firing strength of the ceramsite, but the clay is not easy to be added too much, so that the resources are wasted, and the sintering temperature of the ceramsite is increased.
Municipal sludge due to SiO in fly ash2And Al2O3The content is lower, if only adding clay class material can cause manufacturing cost higher, and the handling capacity of waste incineration fly ash also can not be too high, through adding municipal sludge, can improve the intensity of fly ash haydite, can also improve the handling capacity of waste incineration fly ash.
The cooperation of the waste incineration fly ash, the clay and the municipal sludge improves the strength of the fly ash ceramsite, and only with certain strength, the pore-forming rate of capillary pores can be improved, the strength of the fly ash ceramsite as a carrier is improved, the function of the phase-change ceramsite can be better played, and the problem of preparing the phase-change ceramsite from the waste incineration fly ash is solved.
Moreover, the municipal sludge contains a certain amount of carbon (C), which can play a certain pore-forming role and is beneficial to the formation of pores of the fly ash ceramsite.
The phase change material is loaded in the capillary pores, so that the bonding force between the phase change material and the fly ash ceramsite is favorably improved, the capillary pores have a good effect of solidifying the phase change material, the phase change material is not easy to seep out, the durability of the material is improved, the loading capacity of the phase change material can be improved under a certain number of the capillary pores, and the performance in the phase change aspect is better exerted.
In some embodiments of the invention, the ceramsite material comprises 20-40 parts of raw material waste incineration fly ash, 30-40 parts of clay and 30-50 parts of municipal sludge by weight; further, the ceramsite material comprises 30-40 parts of raw material waste incineration fly ash, 30-40 parts of clay and 30-50 parts of municipal sludge in parts by weight.
The doping amount of the fly ash and the doping amount of the municipal sludge have a synergistic relationship, the doping amount of the fly ash can influence the ignition loss amount of the ceramsite, the higher the doping amount of the wastewater is, the more the proportion of the components with higher ignition loss amount is, and the larger the ignition loss amount of the ceramsite is. The strength and the forming performance of the ceramsite are influenced by the doping amount of the fly ash. The incorporation of fly ash contributes to the reduction of the Cl leaching amount.
The fly ash has great influence on the ceramsite, the strength and the pore structure are maintained, so that the phase-change ceramsite is formed better, and the components in the ceramsite cooperate with each other to reduce the ignition loss.
In some embodiments of the invention, the Fe in the municipal sludge2O3+Na2O+MgO+K2The mass content of O + CaO is 10-15%, and SiO230-40% of Al2O3The mass content of (A) is 10-15%.
In some embodiments of the invention, the phase change material is a paraffin, carboxylic acid or polyol, or the like; further paraffin wax.
In some embodiments of the invention, the fly ash ceramsite has a particle size diameter of 10-20 mm. The particle size diameter of the prepared fly ash ceramsite is kept within a certain range, and the fly ash ceramsite can be better impregnated with the phase change material. The contact area between the capillary pore and the phase-change material is increased, and the effect of filling the capillary pore with the phase-change material is improved.
In some embodiments of the invention, the fly ash ceramsite has a porosity of 50-70%. The porosity of the fly ash ceramsite is controlled through the proportion of the clay and the municipal sludge, the loading capacity of the phase-change material is controlled, and the strength of the fly ash ceramsite is kept in cooperation with the strength of the fly ash ceramsite.
In some embodiments of the present invention, the phase change material is loaded in the phase change ceramic particles at a loading of 48% or more; further 48 to 60 percent. The load capacity of the phase-change material in the phase-change ceramsite can meet the condition that the phase-change enthalpy of the phase-change ceramsite is more than 80J/g, and the phase-change temperature is between 40 and 60 ℃.
In a second aspect, the method for preparing the phase-change ceramsite based on the waste incineration fly ash comprises the following steps:
mixing, granulating and sintering waste incineration fly ash, clay and municipal sludge to obtain fly ash ceramsite;
and soaking the fly ash ceramsite in a liquid phase-change material under vacuum, reducing the pressure to normal pressure, adsorbing and permeating the fly ash ceramsite into the phase-change material, and then obtaining the phase-change ceramsite.
The method for preparing the phase-change ceramsite from the waste incineration fly ash is realized, and the sintering and strength improvement of the ceramsite are promoted by adding the clay and the municipal sludge. By the vacuum impregnation method, gas in the capillary is discharged under vacuum, so that liquid can enter the capillary and can be diffused in the capillary, and meanwhile, the liquid is gathered on the surface of the solid under vacuum and enters the capillary under the action of capillary.
After the pressure is reduced to normal pressure, the fly ash ceramsite gradually permeates into the fly ash ceramsite under the adsorption action of capillary pores. Therefore, the phase-change material can better permeate into the fly ash ceramsite under the actions of comprehensive vacuum impregnation and normal-pressure adsorption.
In some embodiments of the invention, the municipal sludge is dried prior to mixing.
In some embodiments of the invention, the granulation is followed by drying and then sintering, the drying temperature being between 90 ℃ and 120 ℃ and the drying time being between 2.5 h and 5 h.
In some embodiments of the invention, the sintering temperature is 1100-; further, the heating rate is 3-10 ℃/min, the temperature is preserved for 15-40min when the preheating temperature reaches 400 ℃, and then the temperature is heated to 1100-1200 ℃. Furthermore, the sintering temperature is 1130-1150 ℃, and the sintering time is 15-20 min.
The pre-sintering temperature and the sintering temperature affect the strength, the loss on ignition and the water absorption of the ceramsite, and the temperature affects the decomposition reaction of carbonate minerals, organic compounds, iron oxide and the like in the raw materials, gas release and the bulk density. The sintering temperature can influence the formation of the internal structure of the ceramsite, and is favorable for forming a better pore structure. The sintering temperature affects the degree of interfusion of the components.
The sintering time affects the development of the internal structure and the compactness of the internal pore structure
In some embodiments of the invention, the temperature of the vacuum impregnation is greater than or equal to the melting phase transition point of the phase change material; further, the phase-change material is paraffin, and the temperature of vacuum impregnation is greater than or equal to 45-60 ℃. At a temperature greater than or equal to the phase transition point of the phase-change material, the phase-change material is liquid, for example, paraffin is changed from a solid state to a liquid state at a temperature greater than or equal to 45-60 ℃, and the liquid state has better diffusion capacity than the solid state and can infiltrate the solid.
In some embodiments of the invention, the time for vacuum impregnation is 20-80 min; further 30-60 min. The vacuum impregnation time can improve the infiltration amount of the phase-change material.
In some embodiments of the invention, the vacuum is 0.06 to 0.2 MPa; further 0.08 to 0.10 MPa.
In some embodiments of the invention, the time for adsorption infiltration of the phase change material is 50 to 110 minutes; further 60-100 minutes. The adsorption process is a continuation of vacuum impregnation, and the phase-change material can continuously enter the capillary pores in the adsorption process, so that the loading capacity is improved. The adsorption time has a certain relation with the fluidity of the phase-change material such as paraffin and the porosity of the fly ash ceramsite.
The fly ash mixing amount, the preheating temperature, the sintering temperature and the sintering time comprehensively influence the performance of the ceramsite, the optimal technical scheme is comprehensively considered, and the parameter range meets the optimal performance of the ceramsite.
In a third aspect, the phase-change ceramsite based on the waste incineration fly ash is applied to the field of phase-change energy storage.
One or more technical schemes of the invention have the following beneficial effects:
(1) the phase-change energy-storage ceramsite is mainly prepared by taking waste incineration fly ash as a raw material and matching municipal sludge and clay to obtain the fly ash ceramsite and further preparing the phase-change energy-storage ceramsite by taking paraffin as a phase-change material. The invention utilizes the waste incineration fly ash to fire the phase change energy storage ceramsite, and changes the incineration fly ash which is difficult to dispose at present into the building material for resource utilization. On one hand, the disposal cost of the fly ash is greatly reduced, a feasible way is found for safe disposal of the fly ash, and the demand of the ceramsite industry on natural raw materials (such as clay and the like) is reduced; on the other hand, the fly ash ceramsite is prepared into the phase-change ceramsite for building energy conservation, which finds a way for high-valued application of the fly ash ceramsite, and can save energy and reduce emission. And the ceramsite can effectively solidify various heavy metal elements in the fly ash in the sintering process, most of the heavy metals are solidified in the mineral crystal phase of the ceramsite, and dioxin in the fly ash is also thoroughly decomposed in the high-temperature sintering process of the ceramsite. The invention is a breakthrough in the disposal and utilization of waste such as incineration fly ash and the like, and has important significance in the fields of novel building materials and environmental engineering.
(2) The selected fly ash ceramsite is considered to be a good carrier for the organic phase change material. The haydite generally has high porosity and large specific surface area, and can provide a large number of attachment sites for the phase change material. More importantly, the unique network structure in the fly ash ceramsite can effectively prevent the leakage of inorganic salt by virtue of the capillary force and the surface tension of the fly ash ceramsite. The carrier material has the advantages of high temperature resistance, low density, high strength, high porosity and the like, and when the temperature is higher than the melting point of the phase-change material, the composite material can maintain the original shape and has certain mechanical strength and higher energy storage density.
(3) The preparation method of the phase-change energy-storage ceramsite is simple in process, does not need pretreatment of raw materials, and is environment-friendly; the phase change energy storage ceramsite is light in weight, high in strength, high in enthalpy value, good in shaping effect, not easy to leak, good in phase change energy storage effect, small in stacking density, proper in strength, low in phase change temperature of 40-60 ℃ and high in phase change enthalpy value of more than 80J/g, and has a phase change function, and the phase change temperature is suitable and adjustable.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the relationship between the amount of fly ash added and the amount of water added;
FIG. 2 is a relationship between the amount of fly ash and the amount of loss of ceramsite;
FIG. 3 is the effect of the fly ash content on the water absorption of 1h, the bulk density and the barrel pressure strength;
FIG. 4 is an appearance diagram of sintered ceramsite with different amounts of fly ash, (a) is a diagram of different amounts of fly ash, (a) is an enlarged diagram of 40% of the fly ash;
FIG. 5 is a leaching test chart of ceramsite Cl under different fly ash contents;
FIG. 6 is a graph of the effect of preheat temperature on loss on ignition;
FIG. 7 shows the effect of preheating temperature on water absorption at 1 hr, bulk density, and barrel pressure
FIG. 8 is a graph of the effect of sintering temperature on loss on ignition;
FIG. 9 is a graph showing the effect of sintering temperature on water absorption at 1 hour, bulk density, and barrel pressure strength;
FIG. 10 is an appearance diagram of ceramsite under different sintering temperatures;
FIG. 11 is a graph of the effect of sintering time on loss on ignition;
FIG. 12 is a graph showing the effect of sintering time on water absorption at 1 hour, bulk density, and barrel compression strength;
FIG. 13 is a graph showing the effect of process parameters on the loss on firing of ceramic particles;
FIG. 14 shows the effect of process parameters on the water absorption of ceramsite 1h
FIG. 15 is a graph showing the effect of process parameters on the packing density of ceramic particles;
FIG. 16 is the effect of the process parameters on the cylinder pressure strength of the ceramsite.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention will be further illustrated by the following examples
Example 1
The method comprises the following steps: respectively crushing the raw materials by a crusher or a ball mill, and sieving the crushed raw materials by a 100-mesh sieve for later use;
step two: mixing the waste incineration fly ash, clay and dried municipal sludge according to a certain mass ratio to form a mixture. The mass ratio of each component is as follows: 30 parts of waste incineration fly ash, 30 parts of clay and 40 parts of dried sludge.
Step three: weighing a proper amount of water, adding the water into the mixed material, and uniformly stirring to form a mass; then granulating to ensure that the particle size diameter of the ceramsite is between 10 and 20 mm; and (3) placing the agglomerated raw pellets in a glassware, heating and drying in a 105 ℃ oven for 4h, sintering in a muffle furnace at 1150 ℃ for 20-30min, and naturally cooling to obtain the fly ash ceramsite after sintering.
(2) Preparing phase change energy storage ceramsite:
the phase change energy storage ceramsite is prepared by taking paraffin as a phase change material and fly ash ceramsite as a carrier through a vacuum impregnation method. The method comprises the following steps: vacuumizing the fly ash ceramsite for 30-60 minutes at the temperature of 45-60 ℃ of a paraffin phase transition point, wherein the vacuum degree is 0.08-0.10 MPa; adding a molten paraffin phase-change material; raising the pressure to normal pressure to ensure that the liquid paraffin gradually permeates into the fly ash ceramsite, wherein the adsorption and permeation time is 60-100 minutes; and cooling to obtain the paraffin/fly ash ceramsite shape-stabilized phase change material.
The phase transition temperature is 40-60 ℃, and the phase transition enthalpy is above 80J/g.
Example 2
The differences from the embodiment 1 are that the waste incineration fly ash is 40 parts, the clay is 30 parts, and the dried sludge is 30 parts.
The phase transition temperature is 40-60 ℃, and the phase transition enthalpy is above 80J/g.
Example 3
The differences from the embodiment 1 are 20 parts of waste incineration fly ash, 30 parts of clay and 50 parts of dried sludge.
The phase transition temperature is 40-60 ℃, and the phase transition enthalpy is above 80J/g.
Comparative example 1
The differences from the embodiment 1 are 50 parts of waste incineration fly ash, 30 parts of clay and 20 parts of dried sludge.
Comparative example 2
The differences from the embodiment 1 are 10 parts of waste incineration fly ash, 30 parts of clay and 60 parts of dried sludge.
Experimental example 1
1) Influence of fly ash content on ceramsite performance
The doping amount of the fly ash is set to be 10-50%, a sintering system that the heating rate is 7 ℃/min, the temperature is kept at 400 ℃ for 30min, and the temperature is kept at 1150 ℃ for 20min is adopted, the loss on ignition, the bulk density, the water absorption of 1h, the barrel pressure strength and the Cl leaching of the ceramsite are taken as indexes, the influence of the doping amount of the fly ash on the performance of the ceramsite is researched, and the result is shown in Table 1.
Table 1 measurement results of various indexes of ceramsite under single-factor experiment
2) Relationship between fly ash incorporation amount and water addition amount
According to the results of the performance tests of each set of formulas in Table 1, it can be seen that the relationship between the amount of water added and the amount of fly ash increases, the relationship is as shown in FIG. 1, the amount of fly ash and the amount of water added are in negative correlation, the fitted curve is that y is-1.59 x +183.9, and the correlation coefficient R is2Is 0.99814. During the design of the formula, the adding proportion of clay is unchanged, the adding amount of fly ash is increased, the adding amount of municipal sludge is reduced, the difference of the ignition loss amount of the fly ash and the ignition loss amount of the municipal sludge is not too large, but according to the determination of chemical components, the carbon content in the fly ash is 25.08%, the carbon content in the sludge is 40.87%, the increase of the carbon content can increase the using amount of water, so that the less the adding amount of the fly ash is, the more the adding amount of the municipal sludge is, the larger the carbon content in the formula is, and the larger the adding amount of water is.
3) Relationship between fly ash incorporation amount and ceramsite ignition loss
The key to the loss on ignition in the sintering process is C, S, etc. in the raw material, and it can be seen from fig. 2 that the loss on ignition of the ceramsite gradually increases with the increase of the amount of the fly ash. According to the chemical component determination of the raw materials, the fly ash as the main raw material in the ceramsite and the municipal sludge have higher carbon content, and the fly ash also contains more components such as S, Cl and the like besides the higher carbon content. The loss on ignition of fly ash and municipal sludge were measured separately, with 18.2% loss on ignition of fly ash and 16.7% loss on ignition of municipal sludge, which was lower probably because of the lower organic content of the components compared to other municipal sludge. The test result is consistent with the figure, the higher the fly ash content is, the more the component proportion with higher loss on ignition is, and the greater the loss on ignition of the ceramsite is.
4) Relationship between fly ash incorporation amount and ceramsite water absorption rate for 1 hour, bulk density and cylinder pressure strength
The bulk density of the ceramsite is not necessarily related to the water absorption rate of 1 hour and the cylinder pressure strength, the lower the water absorption rate is, the higher the cylinder pressure strength is, but the lower the bulk density can reflect that the internal porosity is possibly rich, the corresponding water absorption rate is higher, and if an excellent ceramsite with the low bulk density, the low water absorption rate of 1 hour and the high cylinder pressure strength is to be obtained, the firing process of the ceramsite needs to be adjusted according to actual conditions. The relationship between the fly ash content and the performance of the ceramsite is explored according to the performance test results of each group of formulas in table 1, as shown in fig. 3.
As can be seen from the analysis of FIG. 3, as the amount of fly ash added increases, the water absorption rate increases after 1 hour, the variation range of bulk density with the amount of fly ash is large, and the barrel pressure strength gradually decreases with the increase of the amount of fly ash added. When the fly ash content is 30%, the water absorption rate of the ceramsite is 0.42% at the lowest level after 1 hour, and the water absorption rate standard of the ceramic is 0.5% according to the standard ISO10545-2, which indicates that the ceramsite doped with the fly ash content has very low apparent porosity and is completely vitrified under the current sintering process. The trend of the bulk density changing along with the increase of the fly ash mixing amount is more complex, and the overall appearance is that the bulk density increases firstly, then decreases, increases finally decreases. The bulk density is closely related to the bulk density of the raw materials and the porosity of the finished product, and the bulk density of the garbage fly ash is measured to be 656.8kg/m3The bulk density of the municipal sludge is 596kg/m3When the mixing amount of the fly ash is increased from 10% to 20% and from 30% to 40%, the mixing amount of the fly ash is increased, so that the bulk density of the ceramsite is higher. The cylinder pressure intensity is in a descending trend along with the increase of the mixing amount of the fly ash. The fly ash contains CaO and SiO2、Al2O3The content of components forming the ceramsite skeleton is less, so when the fly ash content is high, the total SiO in the ceramsite blank is high2、Al2O3The content of the ceramsite is low, and the compression resistance of the ceramsite is naturally reduced. When the fly ash content reaches 50%, SiO in the ceramsite blank2、Al2O3The components are not enough to support the molding of the ceramsite, so the ceramsite is cracked along with the continuous release of gas in the high-temperature sintering process.
The content of fly ash is 30 percentThe municipal sludge mixing amount is 40 percent, the clay mixing amount is 30 percent, the preheating is carried out for 30min at the temperature of 400 ℃, then the temperature is increased to 1150 ℃ and the sintering is carried out for 20min, the cylinder pressure strength is 31.8MPa, and the bulk density is 975.2kg/m3And the water absorption rate of the high-strength sintered ceramsite is 0.42 percent after 1 hour. Under the sintering process, organic components in the raw materials can uniformly and continuously escape through high-temperature pyrolysis to form a rich pore structure, all chemical components in the blank body completely react, and an internal liquid phase melts and escapes at high temperature under the control of a proper sintering process to form a smooth glaze layer (as shown in figure 4) on the surface of the ceramsite, so that the low bulk density and the low water absorption rate for 1 hour of the ceramsite are realized, and the cylinder pressure strength is high.
As can be seen from fig. 4, the ceramsite sintered body shows purple black when the fly ash content is 10% and 20%, and brown yellow when the fly ash content is 30%, as shown in fig. 4(b), when the fly ash content is 40% or more, the color of the ceramsite sintered body basically changes into earthy yellow, because the mixture ratio of the raw materials is different, and the color of the ceramsite finally shows different after the high temperature reaction. It can be seen from fig. 4(a) that when the fly ash content is 50%, the phenomena of unfired (white) and burst of the ceramsite occur, which may be caused by the unstable reaction and burst of the fly ash due to the complex fly ash component and too much fly ash content during the high-temperature sintering process.
5) Relationship between fly ash incorporation amount and Cl leaching amount in ceramsite sintered body
The requirement of the light aggregate and the experimental standard thereof on chloride (calculated by the content of chloride ions) is less than or equal to 0.02 percent. As shown in fig. 5, the amount of Cl leached gradually increased with the increase in the amount of fly ash. When the fly ash content is 30%, the leaching toxicity of Cl is 0.002%, and when the fly ash content reaches 40%, the leaching percentage of Cl is 0.021%, which is slightly out of the standard limit.
The more the fly ash is mixed, the larger the loss on ignition is and the lower the water addition is. The water absorption and bulk density of 1h are complex to change with the increase of the fly ash doping amount, but the fly ash composite material shows excellent performances of lowest bulk density and water absorption of 1h and higher cylinder pressure strength at 30 percent doping amount. When the ceramsite formula with the fly ash content of 40% is selected, the leaching concentration of Cl in the ceramsite exceeds a certain standard by referring to the Cl leaching standard of lightweight aggregate and experimental standards thereof, so that the fly ash with the content of 30% is selected as the optimal content of the ceramsite.
6) Influence of preburning temperature on ceramsite performance
The preheating is carried out in the process of firing the ceramsite, and the preheating mainly reduces the volatilization rate of gas in the raw material balls and prevents the ceramsite from cracking at high temperature due to the too fast volatilization of the gas. When the performance of the raw materials is stable, the preheating temperature in a certain range can not greatly influence the performance of the ceramsite, but the fly ash has more complex components and unstable performance, and the phenomenon of cracking of some ceramsite can be found when the preheating temperature is different in the previous experiment. On the basis of 30% of the doping amount of the fly ash, the influence of the preheating temperature on the performance of the ceramsite is researched, the preheating temperature is set to be 360 ℃, 380 ℃, 400 ℃, 420 ℃ and 440 ℃ according to the approximate preheating range obtained by the previous experiment, other sintering processes are unchanged, and the experimental result is shown in fig. 6.
The loss on ignition represents the amount of gas released from the sample during heating. As can be seen from FIG. 6, the overall tendency of the ignition loss of the ceramsite is first rising and then falling with the rising of the preheating temperature, and according to the measured values, the ignition loss is not much changed with the preheating temperature, mainly from 17.54% to 17.89%, which shows that in the preheating temperature range, the gas can be uniformly released, so that the influence of the preheating temperature on the ignition loss is small.
As shown in FIG. 7, the water absorption rate of the ceramsite is firstly reduced and then increased within 1 hour, the water absorption rate within 1 hour is 0.85% at the preheating temperature of 360 ℃, the water absorption rate within 1 hour is 1.42% at the preheating temperature of 440 ℃, and the water absorption rate of the ceramsite reaches the lowest 0.42% at the preheating temperature of 400 ℃; the change trend of the cylinder pressure strength is just opposite to the water absorption rate of 1h, and the cylinder pressure strength of the ceramsite is highest when the preheating temperature is 400 ℃; the lowest water absorption and the highest cylinder pressure strength indicate that the chemical components in the ceramsite are best fused at the moment, and the internal porosity is the lowest. The bulk density of the ceramsite is firstly reduced, then increased and then reduced, and the change trend of the loss on ignition is opposite to that of the ceramsite; at high temperature, decomposition reaction of organic compounds occurs, and carbonate minerals, iron oxide, and the like in the raw material also undergo decomposition reaction, and the more the gas is released, the smaller the corresponding bulk density may be. At a preheating temperature ofThe lowest stacking density of the ceramsite is 975.2kg/m at 400 DEG C3. In conclusion, the preheating temperature of the single-factor experimental ceramsite is determined to be 400 ℃. At this time, the loss on ignition of the ceramsite was 17.89%, the water absorption rate after 1 hour was 0.42%, and the bulk density was 975.2kg/m3The barrel pressure strength was 31.8 MPa.
7) Influence of sintering temperature on ceramsite properties
The sintering temperature and the strength of the ceramsite have an inseparable relationship, and the selection of an appropriate sintering temperature has the most direct influence on the performance of the ceramsite. In this section, the sintering temperature was set to 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃ and five temperature gradients, and the influence of the sintering temperature on various performances was investigated.
As can be seen from fig. 8, the loss on ignition gradually increases as the sintering temperature increases, and the increase in sintering temperature is more favorable for the vaporization of the organic substances in the raw materials after oxidation, and therefore the loss on ignition gradually increases. FIG. 9 shows that as the sintering temperature is increased from 1130 deg.C to 1150 deg.C, the water absorption rate decreases from 16.89% to 0.42% for 1 hour, the temperature continues to increase, and the water absorption rate fluctuation for 1 hour is small and basically stable, because the ceramsite is completely vitrified when reaching a certain sintering temperature during the sintering process, and the water absorption rate for 1 hour is lower than the standard 0.5% of the ceramic, and at this time, the water absorption rate continues to increase greatly for 1 hour without much change; the bulk density is increased from 784.8kg/m3 to 975.2kg/m3 along with the increase of the sintering temperature from 1130 ℃ to 1150 ℃; along with the increase of the sintering temperature, the liquid phase amount in the ceramsite increases, solid particles in the ceramsite are close to each other due to the surface tension of the liquid phase, and pores generated when organic components are pyrolyzed and volatilized are filled by the molten liquid phase to form a compact ceramsite internal structure, so that when the sintering temperature is 1150 ℃, the 1h water absorption rate of the ceramsite sintered body is low, and the cylinder pressure strength is high. The cylinder pressure strength is increased and then reduced along with the increase of the sintering temperature, the liquid phase generation amount in the ceramsite is more at high temperature, the development of an enamel layer is better, and the compressive strength of the ceramsite is increased along with the increase of the sintering temperature. However, when the temperature is too high, the viscosity inside the ceramsite is reduced due to the generation of a large amount of liquid phase, organic matters are decomposed violently, the escape of gas is not controlled, small gas holes which are originally uniformly distributed become communicated large pores, and finally, the framework of the ceramsite is collapsed, and the strength is reduced.
FIG. 10 is an appearance diagram of ceramsite with 30% loading amount of garbage fly ash at different sintering temperatures, which shows that the ceramsite is light in color and the same ceramsite has different colors at 1130 ℃ because the sintering temperature is too low to fuse the components in the ceramsite with each other, thereby causing insufficient reaction to generate multicolor; the sintering condition of the ceramsite at 1140 ℃ is better than that of the ceramsite at 1130 ℃, but the color difference can be seen, the temperature is continuously increased, when the sintering temperature is 1150-1170 ℃, the color of the whole ceramsite is brown or brown black, the color of the same ceramsite is uniform, and the fact that all components in the ceramsite can be fused with each other and fully react within the temperature range is shown. In summary, the sintering temperature is 1150 ℃ which is the optimum temperature.
8) Influence of sintering time on ceramsite properties
The fly ash content is 30%, different sintering times are set at the preheating temperature of 400 ℃ and the sintering temperature of 1150 ℃, the change trend of the ceramsite performance along with the sintering time is researched, and the experimental results are shown in fig. 11 and 12.
In order to obtain ceramic particles with excellent properties, the ceramic particles are usually kept at the highest sintering temperature for a period of time. As shown in fig. 11 and 12, when the sintering time was increased from 10min to 30min, the ignition loss did not largely float, and the whole showed a rising tendency because the thermal decomposition of the organic matter had progressed almost completely during the temperature rise, and the ignition loss did not largely change as the sintering time was increased. As can be seen from fig. 12, as the sintering time increases, the water absorption rate of 1h shows a decreasing trend, while the change trends of the bulk density and the cylinder pressure strength are substantially the same, and both show an increasing curve, because the sintering time is too short, the internal structure of the ceramsite is loose, and the contact area of the solid-phase particles is small; along with the increase of the sintering time, the reaction inside the ceramsite is sufficient, more liquid phase is generated, and a glass phase or an enamel layer is formed after cooling, so that the internal pores of the ceramsite are compact, the stacking density is increased, the water absorption rate is reduced within 1 hour, and the cylinder pressure strength is increased. When the sintering time is 20min, the water absorption of the ceramsite reaches 0.42% after 1h, and the internal structure of the ceramsite is compact. According to the measurement results of various properties of the ceramsite under different sintering times, the ceramsite is sintered for 20min to obtain the optimal sintering time.
Experimental example 2
The variable is the fly ash mixing amount which is respectively 25 parts, 30 parts and 35 parts.
The variable is the preheating temperature which is respectively 380 ℃, 400 ℃ and 420 ℃.
The variables are sintering temperature which is 1145 ℃, 1150 ℃ and 1155 ℃.
The variable is sintering time which is respectively 15min, 20min and 25 min.
The set of orthogonal experiments is shown in table 2, and the results of the performance tests of the orthogonal experiments are shown in table 3.
TABLE 2 orthogonal experimental table
TABLE 3 results of orthogonal Experimental Performance testing
And (4) analyzing results:
1) loss on ignition
And designing a four-factor three-level orthogonal test, investigating the change condition of the ignition loss under three levels of the four factors, comparing an extreme value and a k value under each level, and combining the characteristics of the ignition loss to deduce the optimal level of the ignition loss.
Table 4 is an orthogonal experimental table using the ignition loss as the index of investigation, where k1, k2, and k3 are the average values of three levels of the four factors set in the orthogonal experiment, and R is the range, i.e. the difference between the maximum value and the minimum value of the same index of investigation. The range represents the degree of dispersion of data, so the larger the range is, the larger the influence of the factor on the index under investigation is.
TABLE 4 Quadrature experiments on loss on ignition
As can be seen from table 4 and fig. 13, RA > RD > RB > RC, the worst is the fly ash loading a, indicating that the influence of the fly ash loading on the loss on ignition is the greatest, and the three levels are 18.6, 17.7 and 17, respectively, the magnitude of the loss on ignition is closely related to the amount of organic components such as C, S contained in the sample, and the larger the loss on ignition is, the more complete the reaction is, and therefore the first level is the optimum level of the loss on ignition. Secondly, the sintering time D has a large influence on the ignition loss, and the extreme difference between the preheating temperature B and the sintering temperature C is 0.1, which shows that the two have the same influence on the ignition loss and the lowest influence level. The influence of various factors is that the fly ash content is larger than the sintering time, the preheating temperature is larger than the sintering temperature, and the optimal scheme is A1B1C1D 2.
2) Water absorption rate
By designing a four-factor three-level orthogonal test, the variation condition of the water absorption of 1h under three levels of the four factors is investigated, and the optimal level of the water absorption of 1h under each factor is deduced by comparing the extreme value and the k value under each level and combining the characteristic of the water absorption of 1 h.
TABLE 51 orthogonal experiment of Water absorption
It is found from table 5 and fig. 14 that the fly ash loading a is the most different of the four factors, where R is 4.18, so that the effect of different levels of fly ash loading on water absorption for 1 hour is the greatest. For the performance of the ceramsite, the smaller the water absorption rate is, the more compact the internal voids of the ceramsite is, i.e., the smaller the water absorption rate is, the better the performance is. The three levels of the factor A are respectively 4.81, 0.63 and 0.97, so that the second level of the fly ash mixing amount is the best, the second maximum extreme value is the preheating temperature, the extreme value is 3.52, and the preheating temperature is the first level; the third maximum is sintering temperature, the extreme value is 2.85, and the first level is adopted; the minimum influence on the water absorption of 1h among the four influencing factors is the sintering time, and the extreme value of the sintering time is a first level. The optimal solution would therefore be A2B1C1D 1.
3) Bulk density of ceramsite
By designing a four-factor three-level orthogonal test, the change condition of the bulk density under three levels of the four factors is inspected, and the optimal level of the bulk density under each factor is deduced by comparing the extreme value and the k value under each level and combining the characteristics of the bulk density. As can be seen from table 6, the R values of the four factors are 63, 35.2, 20.7 and 66, respectively, the greater the range, the greater the dispersion degree of the data, i.e. the greater the influence of the factor on the experiment, it can be known through comparison that the sintering time > fly ash doping amount > preheating temperature > sintering temperature, and the smaller the value is, the better the packing density is, so the optimal level of the sintering time with the maximum range is the third level, the optimal level of the fly ash doping amount is the second level, the optimal level of the preheating temperature is the first level, and the optimal level of the sintering temperature is the third level, therefore, the optimal scheme under the performance research should be A2B1C3D3, and in the orthogonal experiment, the variation range of each factor at each level is as shown in fig. 15.
TABLE 6 Quadrature experiments on bulk Density
4) Cylinder pressure strength of ceramsite
By designing a four-factor three-level orthogonal experiment, the change condition of the cylinder pressure strength under three levels of the four factors is inspected, and the optimal level of the cylinder pressure strength under each factor is deduced by comparing the extreme value and the k value under each level and combining the characteristics of the cylinder pressure strength. Table 7 shows the results of orthogonal experiments on the cylinder compressive strength, and FIG. 16 shows the variation trend of the cylinder compressive strength of the ceramsite at three levels of each parameter, which are combined to find that k isA3>kA1>kA2，kB1>kB2>kB3，kC1>kC2>kC3，kD1>kD2>kD3. Wherein, the influence of the fly ash content on the cylinder pressure strength of the ceramsite is the largest, and the influence of the sintering temperature on the cylinder pressure strength of the ceramsite is the smallest, because the optimum of the ceramsite is researched through single-factor experimentsSintering temperature, the research of the orthogonal experiment on the sintering temperature is to more reasonably distribute energy consumption. Range sorting: RA>RB>RD>RC, various factors influence the amount of fly ash>Preheating temperature>Sintering time>When other properties are unchanged, the larger the cylinder pressure strength of the ceramsite is, the larger the pressure bearing capacity is, so that the optimal scheme is A3B1C1D 1.
TABLE 7 orthogonal experimental table of barrel compression strength
In summary, the most preferred embodiment is A1B1C1D2 for loss on ignition, A2B1C1D1 for 1h water absorption, A2B1C3D3 for bulk density, and A3B1C1D1 for barrel pressure strength. The optimal levels of fly ash mixing amount to ceramsite ignition loss, water absorption rate of 1h, bulk density and cylinder pressure strength are A1, A2, A2 and A3, the most significant to cylinder pressure strength is A3, and the most significant to water absorption rate of 1h and bulk density is A2. One of the most important indexes of the ceramsite performance test is the barrel pressure strength, but the experiment aims at treating the hazardous waste fly ash as much as possible, and comprehensively considers and selects A2 as the optimal fly ash mixing amount level; the optimal levels of the preheating temperature on the loss on ignition, the water absorption rate of 1h, the bulk density and the cylinder pressure strength of the ceramsite are B1, B1, B1 and B1, and the influence of the B1 on four performance indexes is most obvious, so that B1 is selected as the optimal level of the preheating temperature. The optimal levels of sintering temperature on the loss on ignition, water absorption rate for 1h, bulk density and cylinder pressure strength of the ceramsite are C1, C1, C3 and C1, the influence of the sintering temperature C1 on the bulk density is not very obvious, but the influence on other three indexes is most obvious, and therefore C1 is selected as the optimal level. The optimal levels of sintering time on the loss on ignition, the water absorption for 1h, the stacking density and the cylinder pressure strength of the ceramsite are D2, D1, D3 and D1, the level of D1 has the most obvious influence on the water absorption for 1h and the cylinder pressure strength, the influence on the stacking density and the loss on ignition is not very obvious, the influence of preheating temperature on the stacking density is the largest, the loss on ignition is mainly determined by the amount of organic components in the ceramsite blank, and therefore, the D1 is firstly used as the most comprehensive considerationThe excellent level. Finally, the optimal parameters are determined to be A2B1C1D1, namely the fly ash mixing amount is 30%, the preheating temperature is 380 ℃, the sintering temperature is 1150 ℃ and the sintering time is 25 min. As 9 groups of experiments in the orthogonal experiment are not consistent with the optimal scheme, in order to obtain the final experiment result, the experiment is carried out once according to the optimal scheme to obtain the ceramsite with the cylinder pressure strength of 34.90MPa, the water absorption rate of 0.15 percent in 1 hour and the bulk density of 988.2kg/m3And the loss on ignition is 18.2 percent, and at the moment, the fly ash ceramsite meets the requirement of the standard of high-strength light coarse aggregates with the density grade of 1000 in the light aggregates and experimental standards thereof.
The components of the incineration fly ash involved in the above examples are shown in table 8, the main chemical components of clay are shown in table 9, and the main chemical components of municipal sludge are shown in table 10.
TABLE 8 analysis of main chemical components of fly ash from incineration of refuse
TABLE 9 analysis of the main chemical composition of Clay
TABLE 10 analysis of the main chemical composition of municipal sludge
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A phase change ceramsite based on waste incineration fly ash is characterized in that: the method comprises the following specific steps: the fly ash ceramsite comprises 15-45 parts of raw material waste incineration fly ash, 25-45 parts of clay and 25-55 parts of municipal sludge by weight, and the phase-change material is loaded in the capillary structure of the fly ash ceramsite.
2. The waste incineration fly ash-based phase-change ceramsite according to claim 1, wherein: the ceramsite material comprises 20-40 parts of raw material waste incineration fly ash, 30-40 parts of clay and 30-50 parts of municipal sludge by weight; further, the ceramsite material comprises 30-40 parts of raw material waste incineration fly ash, 30-40 parts of clay and 30-50 parts of municipal sludge in parts by weight.
3. The waste incineration fly ash-based phase-change ceramsite according to claim 1, wherein: fe in municipal sludge2O3+Na2O+MgO+K2The mass content of O + CaO is 10-15%, and SiO230-40% of Al2O3The mass content of (A) is 10-15%.
4. The waste incineration fly ash-based phase-change ceramsite according to claim 1, wherein: the phase-change material is paraffin, carboxylic acid or polyalcohol, etc.; further paraffin wax.
5. The waste incineration fly ash-based phase-change ceramsite according to claim 1, wherein: the particle size diameter of the fly ash ceramsite is 10-20 mm;
or the porosity of the fly ash ceramsite is 50-70%.
6. The waste incineration fly ash-based phase-change ceramsite according to claim 1, wherein: in the phase-change ceramsite, the load of the phase-change material is more than or equal to 48 percent; further 48 to 60 percent.
7. The method for preparing phase-change ceramsite based on waste incineration fly ash according to any one of claims 1-6, wherein the method comprises the following steps: the method comprises the following steps:
mixing, granulating and sintering waste incineration fly ash, clay and municipal sludge to obtain fly ash ceramsite;
and soaking the fly ash ceramsite in a liquid phase-change material under vacuum, reducing the pressure to normal pressure, adsorbing and permeating the fly ash ceramsite into the phase-change material, and then obtaining the phase-change ceramsite.
8. The method for preparing phase-change ceramsite based on waste incineration fly ash according to claim 7, wherein the method comprises the following steps: the sintering temperature is 1100-1200 ℃, and the sintering time is 20-30 min; further, the heating rate is 3-10 ℃/min, the temperature is preserved for 15-40min when the preheating temperature reaches 400 ℃, and then the temperature is heated to 1100-1200 ℃.
9. The method for preparing phase-change ceramsite based on waste incineration fly ash according to claim 7, wherein the method comprises the following steps: the temperature of the vacuum impregnation is greater than or equal to the melting phase transition point of the phase-change material; further, the phase-change material is paraffin, and the temperature of vacuum impregnation is greater than or equal to 45-60 ℃;
or, vacuum impregnation time is 20-80 min; further 30-60 min;
or the vacuum degree is 0.06-0.2 MPa; further 0.08 to 0.10 MPa;
or the time for adsorbing and permeating the phase-change material is 50-110 minutes; further 60-100 minutes.
10. Use of the phase-change ceramsite based on waste incineration fly ash according to any one of claims 1-6 in the field of phase-change energy storage.
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