CN109734307B - Method for low-energy-consumption melting and efficient solidification of heavy metals in waste incineration fly ash - Google Patents
Method for low-energy-consumption melting and efficient solidification of heavy metals in waste incineration fly ash Download PDFInfo
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- 238000002844 melting Methods 0.000 title claims abstract description 85
- 230000008018 melting Effects 0.000 title claims abstract description 85
- 238000004056 waste incineration Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 30
- 238000005265 energy consumption Methods 0.000 title claims abstract description 16
- 238000007711 solidification Methods 0.000 title claims abstract description 15
- 230000008023 solidification Effects 0.000 title claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
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Abstract
The invention discloses a method for low-energy-consumption melting and high-efficiency solidification of heavy metals in waste incineration fly ash, which comprises the steps of mixing more than two waste incineration fly ashes to obtain a mixed material; the mixed material is sequentially subjected to hot melting treatment and cooling solidification treatment to obtain a solidified glass body; the method controls CaO and SiO of the waste incineration fly ash through the cooperative treatment of various waste incineration fly ashes2、Al2O3、MgO、Fe2O3The main components form a low melting point melting system, and the solidification degree of heavy metal in the slag is improved, so that the concept of 'treating waste by waste and disposing in coordination' is realized, and the cost of melting treatment of the waste incineration fly ash is reduced.
Description
Technical Field
The invention relates to a method for treating waste incineration fly ash, in particular to a method for realizing low-energy-consumption melting and high-efficiency solidification of heavy metal by melting more than two different waste incineration fly ashes, belonging to the technical field of harmless treatment of waste incineration fly ash.
Background
The municipal solid waste is treated mainly by landfill, incineration, composting and the like, and compared with landfill and composting treatment, the refuse incineration method has the advantages of high volume reduction, high-temperature disinfection and the like, but a toxic by-product, namely refuse incineration fly ash, is generated in the refuse incineration process, is enriched in heavy metals such as Cd, Cr, Cu, Ni, Pb, Zn and the like and high-toxicity dioxin organic carcinogens, and is listed as hazardous waste (belonging to HW18 category), so that the refuse incineration fly ash needs to be subjected to harmless treatment.
At present, the harmless treatment technology of the waste incineration fly ash at home and abroad mainly comprises cement solidification and stabilization treatment, chemical agent treatment and molten vitrification treatment. The fly ash cement solidification and stabilization treatment mode has the advantages of simple equipment and operation and relatively low solidification cost, but the fly ash has serious capacity increase after treatment, and Cd and Cr5+Heavy metals such as Mo and Zn are difficult to be stabilized; the chemical agent treatment has the advantages of high heavy metal stabilization degree, little or no capacity increase and various curing agents, but has the defects that the curing agents have certain selectivity, the synchronous stabilization of various heavy metals is difficult to realize, and the stability of the curing agents to dioxin and dissolved salts is weak; in contrast, the melting solidification technology has the characteristics of high temperature and high efficiency, can effectively decompose dioxin in fly ash, and can effectively prevent heavy metals in glass slag from dissolving out by wrapping the heavy metals in glass gridsThe effect of reducing volume and weight is very obvious.
However, the existing melting and solidifying technology of the fly ash from waste incineration needs higher operation temperature (generally about 1500 ℃), so that the melting and solidifying technology of the fly ash has the defects of high energy consumption and high operation cost, and further popularization and application of the melting and solidifying technology are hindered. Therefore, reducing the melting point of the waste incineration fly ash and saving energy consumption become the subject to be overcome in the process of popularizing the melting solidification technology. The invention patent (publication No. CN106765145A) discloses a fly ash melting method and an additive for melting fly ash, wherein the method comprises the steps of adding the additive into fly ash to reduce the melting temperature of the fly ash, and then sending the fly ash added with the additive into a fly ash plasma melting treatment device for melting treatment; the additive used in the method is pure substance SiO2And Al2O3And the melting temperature is still higher than 1300 ℃. The invention patent (publication No. CN101773709A) discloses a method for adjusting CaO/SiO2A universal method for fixing the heavy metals in the fly ash generated by burning fly ash features that CaO and CaCO are added to the fly ash3Or SiO2Adjusting the alkalinity of the incineration fly ash to be between 0.8 and 1.2, thereby improving the fixation rate of heavy metals in the slag and reducing the melting temperature of the incineration fly ash; the method requires incineration fly ash and added SiO2Grinding to 150 mesh and melting temperature is still up to 1350 ℃. The invention patent (publication No. CN1796011A) discloses a fly ash melting additive for waste incineration treatment, which consists of 30-50% by mass of B2O325-40% of SiO27-20% of CaF27-20% of MgO is ground into 106-2(ii) a The melting additive disclosed by the invention can reduce the melting temperature of the fly ash, but all the additives are pure substances, and the addition of the pure substances further increases the cost of the melting treatment of the fly ash. The invention patent (publication No. CN105251758A) discloses a waste incineration fly ash melting composite fluxing agent, which is prepared by combining the following components in parts by weight: 60-80% of crushed glass and 20-40% of powder B2O3Or powdered CaF2One or two of them; the fly ash meltThe melting composite fluxing agent can reduce the operation temperature of the fly ash melting treatment to below 1100 ℃, but the raw material cost and the manufacturing cost are high, and secondary pollutants containing fluorine are generated.
The above patent technologies mix and melt the fly ash with pure chemicals or other wastes to lower the melting temperature of the fly ash, and although the melting temperature of the fly ash is lowered, the operation temperature of the fly ash melting treatment is still high, and the raw material cost and the manufacturing cost thereof are high, which also hinders the further popularization and application of the method.
Disclosure of Invention
Aiming at the technical problems of the existing melting treatment method of the waste incineration fly ash, the invention aims to provide a method for melting the waste incineration fly ash with low energy consumption and efficiently solidifying heavy metal, which directly regulates and controls the components of the fly ash by the proportion among different fly ashes without introducing any external melting additive, on one hand, improves the digestion capability of the waste fly ash, and reduces the treatment cost of the waste incineration fly ash, thereby realizing the concept of 'treating waste by waste and disposing in coordination', on the other hand, can reduce the melting temperature of the fly ash, reduce the energy consumption, realize vitrification of the fixed heavy metal, and avoid secondary pollution.
In order to realize the technical purpose, the invention provides a method for melting and efficiently solidifying heavy metals by waste incineration fly ash with low energy consumption, which is characterized in that more than two types of waste incineration fly ash are mixed to obtain a mixed material; the mixed material is sequentially subjected to hot melting treatment and cooling solidification treatment to obtain a solidified glass body;
the blending principle of the waste incineration fly ash meets the following requirements of main components and contents in the mixed material: the CaO accounts for 20-30% by mass, and SiO accounts for230-40% of Al2O35-15% of MgO, 1.5-4% of MgO and Fe2O3The mass percentage content is 2-5%.
The low-temperature melting treatment scheme of the waste incineration fly ash provided by the invention is obtained based on a large number of experimental conclusions, and the inventor passes throughA great deal of research is carried out on the main components and the relation between the main components and the melting temperature of the waste incineration fly ash, and the CaO and SiO in the waste incineration fly ash are found2And Al2O3Is the main factor affecting the melting temperature. Thus the inventors have conducted a research on CaO-SiO2-Al2O3A large amount of experimental researches are carried out on a ternary thermal melting system, and CaO-SiO is drawn2-Al2O3The phase diagram of the ternary hot-melt system is shown in FIG. 1, and CaO and SiO in the ternary hot-melt system are summarized through experimental data2And Al2O3The relationship between the composition proportion and the melting temperature is further analyzed by combining a phase diagram, so that the content of CaO in percentage by mass is 20-30%, and SiO is obtained230-40% by mass of Al2O3When the mass percent content is 5-15%, the corresponding CaO-SiO2-Al2O3The ternary heat melting system has the lowest melting temperature which is as low as 1200-1250 ℃. The theory is that the catalyst can be used for CaO and SiO2And Al2O3The waste fly ash with different contents is classified, mixed and adjusted to have main components in a preferred proportion range, so that a waste incineration fly ash melting system can be controlled in a low-temperature melting area, and the low-energy-consumption thermal melting treatment is realized by fully utilizing the self components of waste raw materials. On the basis, further regulating and controlling MgO and Fe2O3The glass phase is formed in the hot-melt system by the components in equal proportion, so that the solidification degree of the heavy metal is improved. Therefore, the components of the fly ash melting system are regulated and controlled according to the optimized batching principle of the fly ash, and the purposes of reducing the melting temperature of the fly ash and efficiently solidifying heavy metals are achieved.
Preferably, the two or more kinds of waste incineration fly ash are derived from waste incineration fly ash having different main components. Mainly CaO and SiO2And Al2O3The waste incineration fly ash with different main components is classified, and then the materials are mixed according to the optimal mixing ratio, so that the components of a fly ash melting system are regulated and controlled, and the purposes of reducing the melting temperature of the fly ash and efficiently solidifying heavy metals are achieved. More preferably two or more kinds of refuse incinerationThe fly ash comes from fluidized bed fly ash and grate furnace fly ash, or from different stages in the waste incineration process and different compositions of fly ash.
In a preferable scheme, in the hot melting treatment process, the temperature is kept for 0.3-1 h at 1200-1250 ℃. In the preferred formulation principle, the temperature of hot melt processing is as low as 1200 ℃, which has significant technical advantages over the prior art. The melting temperature of the mixed fly ash is controlled to be less than 1300 ℃, the decomposition rate of dioxin in the melting process reaches 99% or more, and secondary pollution is prevented.
In a preferable scheme, in the cooling and solidifying treatment process, the cooling speed is not lower than 500 ℃/min. And rapidly cooling the slag obtained after the fly ash is melted to form a vitreous body, wherein the vitreous body is formed by rapidly cooling the slag obtained after melting treatment so as to obtain amorphous vitreous body slag, so that heavy metals are more easily solidified in the vitreous body, and the cooling speed is required to be not lower than 500 ℃/min. The leaching concentration of each heavy metal in the formed vitreous body is as follows: cd <0.001mg/L, Cr <0.005mg/L, As <0.006mg/L, Ni <0.001mg/L, Cu <0.006mg/L, Pb <0.1mg/L, Zn <0.5 mg/L.
Compared with the prior art, the technical scheme of the invention has the advantages that:
1) the invention effectively reduces the melting treatment temperature of the waste incineration fly ash by utilizing the self composition of various waste incineration fly ash through the cooperative treatment of various waste incineration fly ash without adding a melting auxiliary agent additionally, and achieves vitrification consolidation, thereby reducing the energy consumption of the waste incineration fly ash melting treatment process, and simultaneously realizing the effective consolidation of heavy metals such as Pb, Zn, Cu, Cd, Cr, Ni and the like.
2) The method simultaneously treats the fly ash with two or more different compositions by low-temperature melting, improves the consumption capacity of the waste incineration fly ash, avoids the use of additives, reduces the treatment cost of the waste incineration fly ash, and realizes the concept of 'treating waste by waste and treating waste in coordination'.
2. The melting treatment temperature of the invention is lower, the volatilization of heavy metal in the melting process of the waste incineration fly ash can be reduced, and the burden of a tail gas treatment system is lightened.
Drawings
FIG. 1 shows CaO-SiO2-Al2O3Phase diagram of ternary hot melt system.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described in more complete detail with reference to the preferred embodiments, but the scope of the invention is not limited to the specific embodiments described below.
Example 1
The fly ash A and B from different waste incineration plants have the main components and melting temperatures shown in Table 1, the fly ash A and B are mixed together in a ratio of 1:5 according to the determined optimized batching principle, then the mixture is put into a melting device for melting treatment, the melting temperature is 1200 ℃, the heat preservation time is 1h, and the molten slag after melting treatment is put into liquid nitrogen for cooling at the cooling speed of 500 ℃/min.
The components and melting temperatures of the fly ash after mixing are shown in table 1, and it can be seen from table 1 that: the content of CaO in the fly ash after mixing is 20.96 percent and SiO232.36% of Al2O39.05% of MgO, 1.52% of Fe2O33.38%, compared to the molten fly ash A alone (>1500 ℃ and B: (B)>1280 ℃) is obviously reduced; and (3) detecting the leaching toxicity of the slag, and knowing that the leaching concentration of each heavy metal in the slag leachate is as follows: cd [ Cd ]<0.0002mg/L、Cr<0.001mg/L、As<0.006mg/L、Ni<0.001mg/L、Cu<0.006mg/L、Pb<0.05mg/L、Zn<0.209mg/L。
TABLE 1 Main Components of different fly ashes and their melting temperatures
Example 2:
the fly ash C and D from different garbage incineration plants have the main components and melting temperatures shown in Table 2, the fly ash C and D are mixed together in a ratio of 1:5 according to the determined optimized batching principle, then the mixture is put into a melting device for melting treatment, the melting temperature is 1200 ℃, the heat preservation time is 0.3h, the molten slag after melting treatment is put into liquid nitrogen for cooling, and the cooling speed is 650 ℃/min.
The components and melting temperatures of the fly ash after mixing are shown in table 2, and it can be seen from table 2 that: the content of CaO in the fly ash after mixing is 21.07 percent and SiO in the fly ash after mixing236.76% of Al2O36.58% of MgO, 1.53% of Fe2O34.70% compared to molten fly ash C alone (C: (B))>1450 ℃ and D: (>1300 ℃) are obviously reduced; and (3) detecting the leaching toxicity of the slag, and knowing that the leaching concentration of each heavy metal in the slag leachate is as follows: cd [ Cd ]<0.0002mg/L、Cr<0.001mg/L、As<0.006mg/L、Ni<0.001mg/L、Cu<0.006mg/L、Pb<0.04mg/L、Zn<0.105mg/L。
TABLE 2 Main Components of different fly ashes and their melting temperatures
Example 3:
the waste incineration fly ash a and B were mixed together at a ratio of 2:1, and the fly ash C and D were mixed together at a ratio of 3:1 to obtain mixed fly ash E and F, respectively, whose main components and melting temperatures are shown in table 3, and as can be seen from table 3: the content of CaO in the mixed fly ash E, F is 32.86 percent and 38.58 percent respectively, and SiO2Respectively 16.62% and 14.14%, Al2O3The contents of the fly ash and the fly ash are respectively 4.23 percent and 2.34 percent, and the CaO and the SiO of the two kinds of mixed fly ash2、Al2O3The content of the fly ash does not meet the blending principle of the fly ash (the content of CaO is 20-30 percent, and SiO is230-40% of Al2O3The content is 5-15%), and the melting temperature of the two mixed fly ashes is more than 1500 ℃.
TABLE 3 Main Components of different fly ashes and their melting temperatures
Claims (5)
1. A method for low-energy-consumption melting and high-efficiency solidification of heavy metals in waste incineration fly ash is characterized by comprising the following steps: more than two kinds of waste incineration fly ash are mixed to obtain a mixed material; the mixed material is sequentially subjected to hot melting treatment and cooling solidification treatment to obtain a solidified glass body; the blending principle of the waste incineration fly ash meets the following requirements of main components and contents in the mixed material: the CaO accounts for 20-30% by mass, and SiO accounts for230-40% of Al2O35-15% of MgO, 1.5-4% of MgO and Fe2O3The mass percentage content is 2-5%.
2. The method for melting and solidifying heavy metals with low energy consumption and high efficiency by using fly ash from waste incineration as claimed in claim 1, wherein: the two or more kinds of waste incineration fly ash are derived from waste incineration fly ash with different main components.
3. The method for melting and solidifying heavy metals with low energy consumption and high efficiency by using fly ash from waste incineration as claimed in claim 2, wherein: the more than two kinds of waste incineration fly ash come from fluidized bed fly ash and grate furnace fly ash or fly ash with different compositions at different stages in the waste incineration process.
4. The method for melting and solidifying heavy metals with low energy consumption and high efficiency by using fly ash from waste incineration as claimed in claim 1, wherein: in the hot melting treatment process, the temperature is kept for 0.3-1 h at 1200-1250 ℃.
5. The method for melting and solidifying heavy metals with low energy consumption and high efficiency by using fly ash from waste incineration as claimed in claim 1, wherein: and in the cooling and solidifying process, the cooling speed is not lower than 500 ℃/min.
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| Title |
|---|
| Preparation of low melting temperature glass ceramics from municipal waste incineration fly ash;Yang J K，Bo X，Boccaccini A;《Fuel》;20090119;全文 * |
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