CN108640523B - Method for preparing microcrystalline glass by using waste incineration ash and acid-washing sludge - Google Patents

Abstract

The invention belongs to the field of solid waste resource utilization, and discloses a method for preparing microcrystalline glass by using waste incineration ash and acid-washing sludge. The method takes waste incineration ash as a main raw material, acid-washing sludge as a nucleating agent, adopts high-temperature melting to obtain base glass, and obtains the microcrystalline glass through one-step heat treatment. The invention realizes harmless disposal and high-value utilization of waste incineration ash and acid pickling sludge, prepares the glass ceramics by a melting-one-step heat treatment method, and has the advantages of short process flow, energy saving, consumption reduction and easy industrialization.

Description

Method for preparing microcrystalline glass by using waste incineration ash and acid-washing sludge

Technical Field

The invention belongs to the field of comprehensive utilization of solid waste resources, and particularly discloses a method for preparing microcrystalline glass by using waste incineration ash and acid-washing sludge.

Background

With the popularization of the waste incineration technology in China, the disposal of waste incineration ash restricts the development of the waste incineration industry. The incineration of garbage produces 20 wt% bottom ash and 4 wt% fly ash, collectively known as garbage incineration ash, which is classified as HW18 hazardous solid waste because of its heavy metals and dioxins.

At present, the waste incineration ash generally adopts disposal modes such as seepage-proofing landfill, cement solidification, melting solidification and the like. The anti-seepage landfill occupies a large amount of land, soil and underground water resources are easily polluted, and air pollution is caused by dioxin escape; the cement curing method causes environmental risks due to unstable heavy metals, dioxin enriched in dedusting ash and the like; the melting and solidifying method is used for vitrifying the waste incineration ash, so that the heavy metal glass is solidified, but the resource utilization is not realized. Therefore, the harmless disposal and resource utilization of the waste incineration ash become important problems to be solved urgently in the waste incineration industry.

In order to solve the problems, research on the preparation of microcrystalline glass by vitrification, nucleation, crystallization and the like by using waste incineration fly ash as a main raw material, and the stable solidification of heavy metal and the high-temperature decomposition, detoxification and solidification of dioxin are realized. The traditional methods for preparing the microcrystalline glass are a melting-sintering method and a melting-two-step heat treatment method. The melting-sintering method is to carry out water quenching, grinding, pressing and sintering on high-temperature melt to obtain the microcrystalline glass. The Chinese invention patent (CN106396411A) discloses a preparation method of microcrystalline glass, which is to mix and melt garbage fly ash and silica sand and prepare the microcrystalline glass by a melting-sintering method. The method for preparing the microcrystalline glass has long existing processHigh energy consumption, low density of the glass ceramics and the like. The melting-two-step heat treatment method is to cast and form high-temperature melt, nucleate, crystallize and anneal to prepare the glass ceramics. The Chinese invention patent (CN102531389A) discloses a method for preparing microcrystalline glass by melting waste incineration fly ash in an electric arc furnace, which takes the waste incineration fly ash after water washing treatment as the main raw material and a nucleating agent TiO₂、Cr₂O₃The microcrystalline glass is prepared by adopting a melting-two-step heat treatment method, the process continuity is good, but the microcrystalline glass comprises two heat treatment stages, the process flow is long, and the energy consumption is high.

In conclusion, the microcrystalline glass prepared by utilizing the waste incineration ash has the problems of high cost, high energy consumption, long process flow and the like. Therefore, the development of a method for preparing microcrystalline glass from waste incineration ash is urgently needed to change waste incineration ash into valuable and turn the danger into safety.

Disclosure of Invention

Aiming at the technical problems, the invention provides a method for preparing microcrystalline glass by using waste incineration ash and acid-washing sludge, which can realize the short-flow, low-energy-consumption and pollution-free preparation of microcrystalline glass by using the waste incineration ash and the acid-washing sludge.

The invention is realized by the following technical scheme:

a method for preparing microcrystalline glass by using waste incineration ash and acid-washing sludge in cooperation comprises the steps of mixing fly ash, bottom ash and acid-washing sludge generated by waste incineration, obtaining base glass by adopting high-temperature melting and forming, and obtaining microcrystalline glass by one-step heat treatment through nucleation and crystallization; the fly ash provides a calcium source for the microcrystalline glass, the bottom ash provides a silicon source for the microcrystalline glass, and the acid-washing sludge is used as a nucleating agent and a fluxing agent for preparing the microcrystalline glass.

Further, when mixing, the mass percentages of all the materials are controlled as follows: 0-50 wt% of waste incineration fly ash, 30-80 wt% of waste incineration bottom ash and 3-20 wt% of acid-washing sludge, and the total amount is 100 wt%.

Further, in the mixture obtained by mixing the fly ash, bottom ash and acid-washing sludge generated by the waste incineration, CaO is 0-25 wt%, and SiO is₂12 to 35 weight percent of Al₂O₃9 to 20 weight percent, K₂O is 4 to 8 weight percent and Na₂3 to 7 weight percent of O and CaF₂2 to 8 weight percent of Fe₂O₃4 to 10 weight percent of Cr₂O₃0.5 wt% to 5 wt%.

Further, the method specifically comprises the following steps:

(1) mixing: uniformly mixing the waste incineration fly ash, the bottom ash and the acid-washing sludge; when mixing, the mass percentages of all the materials are controlled as follows: 0-50 wt% of waste incineration fly ash, 30-80 wt% of waste incineration bottom ash and 3-20 wt% of acid-washing sludge, the total amount is 100 wt%;

(2) melting: melting the uniformly mixed raw materials into a glass melt at 1300-1600 ℃, and keeping the temperature for 0.5-3 h;

(3) forming: obtaining base glass by rolling or floating the melt;

(4) nucleation and crystallization one-step heat treatment: and carrying out one-step heat treatment on the base glass to obtain the microcrystalline glass, controlling the temperature of the one-step heat treatment to be 700-900 ℃, and keeping the temperature for 1-3 h.

Further, the fly ash comprises 40-50 wt% of CaO and K₂12 to 20 weight percent of O and Na₂12-20 wt% of O; the bottom ash comprises SiO₂40 to 50 weight percent; the acid-washing sludge comprises CaF₂ 35wt％～45wt％、Fe₂O₃25 wt% -35 wt% and Cr₂O₃2.5wt％～5wt％。

The principle of the invention is as follows:

1) the oxide in the waste incineration ash is CaO and K₂O、Na₂O、SiO₂、Fe₂O₃MgO and Al₂O₃Etc.; wherein CaO in the fly ash is about 45 wt%, and K₂O and Na₂O is about 15 wt% and provides a calcium source for the microcrystalline glass; SiO in bottom ash₂About 45 wt% to provide silicon source for microcrystalline glass;

2) acid-washing sludge containing CaF₂ 35wt％～45wt％、Fe₂O₃25 wt% -35 wt% and Cr₂O₃0.5 wt% -5 wt%, can be used asNucleating agents for glass ceramics, CaF₂And is also a flux.

Therefore, the preparation of the glass ceramics by the cooperation of the waste incineration ash and the acid-washing sludge is scientifically feasible. In the invention, in order to realize the short-flow preparation of the microcrystalline glass, the two procedures of nucleation and crystallization are combined into one procedure to carry out one-step heat treatment, and the key of the technology is to reduce the temperature difference between nucleation and crystallization. By Na in the ash generated by burning garbage₂O and K₂The O is used as a network exosome of the microcrystalline glass, has a certain effect on crystallization of the glass, reduces crystallization activation energy, increases the driving force of crystallization to promote crystallization, thereby reducing crystallization temperature, reducing the temperature difference between nucleation and crystallization, and realizing the preparation of the microcrystalline glass by a melting-one-step heat treatment method.

The invention has the beneficial technical effects that:

(1) the method takes CaO in the waste incineration fly ash as a calcium source of the microcrystalline glass, and SiO in bottom ash₂As a silicon source of the microcrystalline glass, the silicon source meets the component requirements of basic glass;

(2) the method of the invention uses CaF in acid-washing sludge₂、Fe₂O₃And Cr₂O₃As nucleating agents for glass ceramics, CaF₂Meanwhile, the product also serves as a fluxing agent, so that the melting temperature is reduced;

(3) the method uses Na in the waste incineration ash residue₂O and K₂The O is used as a network exosome of the microcrystalline glass, so that the crystallization activation energy is reduced, the crystallization driving force is increased, the temperature difference between nucleation and crystallization is reduced, the microcrystalline glass is prepared by a melting-one-step heat treatment method, the process flow is shortened, and the energy consumption is reduced;

(4) the method realizes harmless disposal and high-value utilization of the waste incineration ash and the acid-washing sludge.

Drawings

FIG. 1 is a schematic view of a process flow for preparing glass ceramics by using waste incineration ash and acid-washing sludge in cooperation in an embodiment of the invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.

Example 1

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 10 wt% of waste incineration fly ash, 80 wt% of bottom ash and 10 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 4 wt%, and SiO is₂35 wt% of Al₂O₃9 wt%, K₂5 wt% of O and Na₂O is 4 wt%, CaF₂3.5 wt.% of Fe₂O₃6 wt% of Cr₂O₃Is 0.6 wt%. The mixture is heated to 1300 ℃ and then is kept warm for 0.5h to obtain a glass melt. And (3) carrying out calendering molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 800 ℃ for 2 hours, and cooling to room temperature to obtain a microcrystalline glass product.

Example 2

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 0 wt% of waste incineration fly ash, 80 wt% of bottom ash and 20 wt% of acid-washed sludge to obtain a mixture, wherein SiO is₂35 wt% of Al₂O₃Is 12 wt%, K₂O is 4 wt%, Na₂O is 3 wt%, CaF₂8 wt% of Fe₂O₃4 wt% of Cr₂O₃Is 5 wt%. The mixture is heated to 1600 ℃ and then is kept warm for 1.0h to obtain a glass melt. The glass melt is rolled and formed to obtain base glass, and the base glass is subjected to one-step nucleation and crystallization heat treatment at the temperature of 832 DEG CCooling to room temperature after 1.0h to obtain the glass ceramic product.

Example 3

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 11 wt% of waste incineration fly ash, 76 wt% of bottom ash and 13 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 4.5 wt%, and SiO is₂32 wt% of Al₂O₃15 wt%, K₂O4.2 wt% and Na₂O is 3.2 wt%, CaF₂4 wt% of Fe₂O₃5 wt% of Cr₂O₃Is 4 wt%. The mixture was heated to 1370 ℃ and then incubated for 2.0h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 864 ℃ for 2.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 4

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 20 wt% of waste incineration fly ash, 63 wt% of bottom ash and 17 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 9 wt%, and SiO is₂30 wt% of Al₂O₃17 wt%, K₂O is 6 wt% and Na₂5 wt% of O and CaF₂7.2 wt.% of Fe₂O₃6 wt% of Cr₂O₃It was 4.5% by weight. The mixture is heated to 1380 ℃ and then is kept warm for 1.5h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 896 ℃ for 1.5h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 5

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 31 wt% of waste incineration fly ash, 55 wt% of bottom ash and 14 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 15 wt%, and SiO is₂29 wt% of Al₂O₃10 wt%, K₂5 wt% of O and Na₂O is 4 wt%, CaF₂4.1 wt.% of Fe₂O₃Is 7 weight percent of the total weight of the alloy,Cr₂O₃it was 4.1% by weight. The mixture was heated to 1393 ℃ and then held for 3.0h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 860 ℃ for 3.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 6

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 40 wt% of waste incineration fly ash, 40 wt% of bottom ash and 20 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 16 wt%, and SiO is₂17 wt% of Al₂O₃11 wt%, K₂O is 6 wt% and Na₂5 wt% of O and CaF₂8 wt% of Fe₂O₃9 wt% of Cr₂O₃Is 5 wt%. The mixture is heated to 1400 ℃ and then is kept warm for 2.5h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 700 ℃ for 2.5h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 7

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 8 wt% of waste incineration fly ash, 76 wt% of bottom ash and 16 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 10 wt%, and SiO is₂32 wt% of Al₂O₃Is 12 wt%, K₂O4.4 wt%, Na₂O is 3.4 wt%, CaF₂6 wt% of Fe₂O₃9.5 wt%, Cr₂O₃It was 4.4% by weight. The mixture was heated to 1410 ℃ and then incubated for 1.8h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 780 ℃ for 1.8h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 8

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 15 wt% of waste incineration fly ash, 70 wt% of bottom ash and 3 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 10.5 wt%, and Si is contained in the mixtureO₂31.5 wt% of Al₂O₃9.5 wt%, K₂5.2 wt% of O and Na₂O4.2 wt%, CaF₂2 wt% of Fe₂O₃10 wt% of Cr₂O₃Is 0.5 wt%. The mixture was heated to 1426 ℃ and then incubated for 1.7h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 900 ℃ for 1.7h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 9

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 23 wt% of waste incineration fly ash, 64 wt% of bottom ash and 13 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 13 wt%, and SiO is₂30.5 wt% of Al₂O₃16.5 wt%, K₂5.5 wt% of O and Na₂O4.5 wt%, CaF₂4.2 wt.% of Fe₂O₃9 wt% of Cr₂O₃It was 4.1% by weight. The mixture was heated to 1435 ℃ and then incubated for 1.8h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 800 ℃ for 2.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 10

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 48 wt% of waste incineration fly ash, 43 wt% of bottom ash and 9 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 24 wt%, and SiO is₂18 wt% of Al₂O₃16 wt%, K₂O7.8 wt%, Na₂O is 6.8 wt%, CaF₂3.5 wt.% of Fe₂O₃8 wt% of Cr₂O₃Is 1 wt%. The mixture was heated to 1440 ℃ and then incubated for 2.1h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 863 ℃ for 1.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 11

The embodiment of the invention providesThe method for preparing the glass ceramics by cooperating the waste incineration ash with the acid-washing sludge comprises the following steps: uniformly mixing 45 wt% of waste incineration fly ash, 40 wt% of bottom ash and 15 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 23 wt%, and SiO is₂20 wt% of Al₂O₃15 wt%, K₂O7.5 wt%, Na₂O is 6.5 wt%, CaF₂5.9 wt.% of Fe₂O₃8.5 wt%, Cr₂O₃It was 4.2% by weight. Heating the mixture to 1450 ℃, and then preserving the heat for 2.5h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out 890 ℃ one-step nucleation and crystallization heat treatment for 2.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 12

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 9 wt% of waste incineration fly ash, 73 wt% of bottom ash and 18 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 3.8 wt%, and SiO is₂32 wt% of Al₂O₃10 wt%, K₂4.3 wt% of O and Na₂O is 3.3 wt%, CaF₂7.6 wt% Fe₂O₃9 wt% of Cr₂O₃It was 4.7% by weight. The mixture is heated to 1469 ℃ and then is subjected to heat preservation for 2.6 hours to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 830 ℃ for 1.5h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 13

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 11 wt% of waste incineration fly ash, 73 wt% of bottom ash and 16 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 4.6 wt%, and SiO is₂31.8 wt% of Al₂O₃10.8 wt%, K₂O4.8 wt%, Na₂O is 3.8 wt%, CaF₂6.3 wt.% of Fe₂O₃4.9 wt%, Cr₂O₃It was 4.7% by weight. The mixture was heated to 1470 ℃ and then held for 2.9h to obtain a glass melt. Forming the glass melt by the float methodAnd carrying out one-step nucleation and crystallization heat treatment at 810 ℃ for 3.0h on the base glass, and cooling to room temperature to obtain the microcrystalline glass product.

Example 14

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 19 wt% of waste incineration fly ash, 69 wt% of bottom ash and 12 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 8.8 wt%, and SiO is₂29 wt% of Al₂O₃19 wt% and K₂5.6 wt% of O and Na₂O4.6 wt%, CaF₂6 wt% of Fe₂O₃5.2 wt%, Cr₂O₃Is 4 wt%. Heating the mixture to 1480 ℃ and then preserving the heat for 3.0h to obtain the glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 888 ℃ for 2.5h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 15

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 27 wt% of waste incineration fly ash, 69 wt% of bottom ash and 4 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 14 wt%, and SiO is₂29.5 wt% of Al₂O₃17.8 wt%, K₂O6.2 wt%, Na₂O5.2 wt%, CaF₂2.1 wt.% of Fe₂O₃6.1 wt%, Cr₂O₃Is 0.6 wt%. The mixture is heated to 1496 ℃ and then is insulated for 1.0h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 864 ℃ for 1.8h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 16

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 35 wt% of waste incineration fly ash, 50 wt% of bottom ash and 15 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 21 wt%, and SiO is₂25 wt% of Al₂O₃16 wt%, K₂O6.5 wt%, Na₂5.5 wt% of O and CaF₂6 wt% of Fe₂O₃4.5 wt%, Cr₂O₃It was 4.3% by weight. The mixture is heated to 1500 ℃ and then is kept warm for 1.6h to obtain glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 896 ℃ for 2.9h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 17

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 43 wt% of waste incineration fly ash, 50 wt% of bottom ash and 7 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 24 wt%, and SiO is₂25.5 wt% of Al₂O₃19 wt% and K₂O7.2 wt%, Na₂O6.2 wt%, CaF₂3.5 wt.% of Fe₂O₃6 wt% of Cr₂O₃Is 0.9 wt%. The mixture was heated to 1510 ℃ and then incubated for 2.2h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 860 ℃ for 3.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 18

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 46 wt% of waste incineration fly ash, 49 wt% of bottom ash and 5 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 24.5 wt%, and SiO is₂24.8 wt% of Al₂O₃18.5 wt%, K₂O7.6 wt%, Na₂O is 6.6 wt%, CaF₂2.6 wt.% of Fe₂O₃6.3 wt%, Cr₂O₃Is 0.8 wt%. The mixture is heated to 1527 ℃ and then is kept warm for 2.8h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 700 ℃ for 1.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 19

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: incinerating garbage50 wt% of burning fly ash, 30 wt% of bottom ash and 20 wt% of acid-washing sludge are uniformly mixed to obtain a mixture, wherein CaO is 25 wt%, and SiO is₂14 wt% of Al₂O₃20 wt%, K₂O8 wt%, Na₂7 wt% of O and CaF₂8 wt% of Fe₂O₃7.2 wt%, Cr₂O₃Is 5 wt%. The mixture was heated to 1530 ℃ and then incubated for 1.0h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 780 ℃ for 1.6h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 20

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 8 wt% of waste incineration fly ash, 79 wt% of bottom ash and 13 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 3.5 wt%, and SiO is₂34.8 wt% of Al₂O₃9.3 wt%, K₂4.3 wt% of O and Na₂O is 3.3 wt%, CaF₂5 wt% of Fe₂O₃6 wt% of Cr₂O₃It was 4.2% by weight. The mixture was heated to 1540 ℃ and then incubated for 1.5h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out 900 ℃ one-step nucleation and crystallization heat treatment for 2.6h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 21

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 12 wt% of waste incineration fly ash, 76 wt% of bottom ash and 12 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 5.6 wt%, and SiO is₂34 wt% of Al₂O₃9.5 wt%, K₂O4.9 wt%, Na₂O is 3.9 wt%, CaF₂4.9 wt.% of Fe₂O₃4.9 wt%, Cr₂O₃Is 4 wt%. The mixture was heated to 1550 ℃ and then incubated for 2.6h to obtain a glass melt. Forming the glass melt by a float method to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 800 ℃ for 2.9h, and cooling to room temperature to obtain a microcrystalline glass product。

Example 22

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 16 wt% of waste incineration fly ash, 73 wt% of bottom ash and 11 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 11 wt%, and SiO is₂33.9 wt% of Al₂O₃11 wt%, K₂5 wt% of O and Na₂O is 4 wt%, CaF₂4.7 wt.% of Fe₂O₃9.1 wt%, Cr₂O₃It was 3.5% by weight. The mixture is heated to 1560 ℃ and then is kept warm for 2.9h to obtain glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 863 ℃ for 3.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 23

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 20 wt% of waste incineration fly ash, 70 wt% of bottom ash and 10 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 13 wt%, and SiO is₂32 wt% of Al₂O₃13 wt%, K₂5.4 wt% of O and Na₂O4.4 wt%, CaF₂4 wt% of Fe₂O₃5.5 wt%, Cr₂O₃It was 3.5% by weight. The mixture was heated to 1573 ℃ and then incubated for 3.0h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out 890 ℃ one-step nucleation and crystallization heat treatment for 1.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 24

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 24 wt% of waste incineration fly ash, 67 wt% of bottom ash and 9 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 14.5 wt%, and SiO is₂31.7 wt% of Al₂O₃15 wt%, K₂5.5 wt% of O and Na₂O4.5 wt%, CaF₂3.6 wt% of Fe₂O₃8.2 wt%, Cr₂O₃Is 1.2 wt%. Heating the mixture to 1580 ℃, and then preserving the heat for 1.0h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 830 ℃ for 1.6h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 25

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 29 wt% of waste incineration fly ash, 55 wt% of bottom ash and 16 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 15 wt%, and SiO is₂28.5 wt% of Al₂O₃14.5 wt%, K₂5.6 wt% of O and Na₂O4.6 wt%, CaF₂7.1 wt% Fe₂O₃4.6 wt%, Cr₂O₃Is 3 wt%. The mixture was heated to 1590 ℃ and then incubated for 1.6h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 900 ℃ for 2.2h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 26

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 32 wt% of waste incineration fly ash, 50 wt% of bottom ash and 18 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 15.5 wt%, and SiO is₂28 wt% of Al₂O₃16 wt%, K₂5.8 wt% of O and Na₂O4.8 wt%, CaF₂7.2 wt.% of Fe₂O₃7.1 wt%, Cr₂O₃It was 4.4% by weight. The mixture is heated to 1600 ℃ and then is kept warm for 2.2h to obtain glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 851 ℃ for 2.8h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 27

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 39 wt% of waste incineration fly ash, 50 wt% of bottom ash and 11 wt% of acid-washing sludge to obtain a mixture, wherein 17 wt% of CaO,SiO₂27 wt% of Al₂O₃16.3 wt%, K₂O6.5 wt%, Na₂5.5 wt% of O and CaF₂4.3 wt.% of Fe₂O₃6.8 wt%, Cr₂O₃Is 2 wt%. The mixture was heated to 1355 ℃ and then incubated for 2.8h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 900 ℃ for 1.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 28

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 42 wt% of waste incineration fly ash, 52 wt% of bottom ash and 6 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 24 wt%, and SiO is₂27.5 wt% of Al₂O₃17 wt%, K₂O7 wt%, Na₂O is 6 wt%, CaF₂2.7 wt.% of Fe₂O₃8 wt% of Cr₂O₃Is 1.2 wt%. The mixture was heated to 1475 ℃ and then held for 1.0h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 889 ℃ for 1.5h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 29

The embodiment of the invention provides a method for preparing microcrystalline glass by cooperating waste incineration ash with acid-washing sludge, which comprises the following steps: uniformly mixing 50 wt% of waste incineration fly ash, 30 wt% of bottom ash and 20 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 25 wt%, and SiO is₂12 wt% of Al₂O₃20 wt%, K₂O8 wt%, Na₂7 wt% of O and CaF₂8 wt% of Fe₂O₃5 wt% of Cr₂O₃Is 5 wt%. The mixture was heated to 1595 ℃ and then incubated for 2.0h to obtain a glass melt. And carrying out float forming on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 865 ℃ for 3.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Example 30

The embodiment of the invention provides aThe method for preparing the glass ceramics by cooperating the waste incineration ash with the acid-washing sludge specifically comprises the following steps: uniformly mixing 31 wt% of waste incineration fly ash, 49 wt% of bottom ash and 20 wt% of acid-washed sludge to obtain a mixture, wherein CaO is 19 wt%, and SiO is₂17 wt% of Al₂O₃15.5 wt%, K₂5 wt% of O and Na₂O is 4 wt%, CaF₂8 wt% of Fe₂O₃4 wt% of Cr₂O₃Is 5 wt%. The mixture is heated to 1495 ℃ and then is kept warm for 1.5h to obtain a glass melt. And carrying out calendaring molding on the glass melt to obtain base glass, carrying out one-step nucleation and crystallization heat treatment at 840 ℃ for 1.0h, and cooling to room temperature to obtain a microcrystalline glass product.

Claims (2)

1. A method for preparing microcrystalline glass by using waste incineration ash and acid pickling sludge is characterized in that fly ash, bottom ash and acid pickling sludge generated by waste incineration are mixed, high-temperature melting and forming are adopted to obtain base glass, and the base glass is subjected to nucleation crystallization and one-step heat treatment to obtain microcrystalline glass; the fly ash provides a calcium source for the microcrystalline glass, the bottom ash provides a silicon source for the microcrystalline glass, and the acid-washing sludge is used as a nucleating agent and a fluxing agent for preparing the microcrystalline glass;

when mixing, the mass percentages of all the substances are controlled as follows: 0-50 wt% of waste incineration fly ash, 30-80 wt% of waste incineration bottom ash and 3-20 wt% of acid-washing sludge, the total amount is 100 wt%;

mixing fly ash, bottom ash and acid-washing sludge generated by waste incineration to obtain a mixture, wherein CaO accounts for 0-25 wt%, and SiO accounts for₂12 to 35 weight percent of Al₂O₃9 to 20 weight percent, K₂O is 4 to 8 weight percent and Na₂3 to 7 weight percent of O and CaF₂2 to 8 weight percent of Fe₂O₃4 to 10 weight percent of Cr₂O₃0.5 wt% to 5 wt%.

2. The method for preparing the glass ceramics by using the waste incineration ash and the acid pickling sludge in cooperation with the acid pickling sludge as claimed in claim 1, which is characterized by comprising the following steps:

(1) mixing: uniformly mixing the waste incineration fly ash, the bottom ash and the acid-washing sludge; when mixing, the mass percentages of all the materials are controlled as follows: 0-50 wt% of waste incineration fly ash, 30-80 wt% of waste incineration bottom ash and 3-20 wt% of acid-washing sludge, the total amount is 100 wt%;

(2) melting: melting the uniformly mixed raw materials into a glass melt at 1300-1600 ℃, and keeping the temperature for 0.5-3 h;

(3) forming: obtaining base glass by rolling or floating the melt;

(4) nucleation and crystallization one-step heat treatment: and carrying out one-step heat treatment on the base glass to obtain the microcrystalline glass, controlling the temperature of the one-step heat treatment to be 700-900 ℃, and keeping the temperature for 1-3 h.

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