CN116283094A - Cooperative treatment method and system for waste incineration fly ash and silicon-rich waste - Google Patents
Cooperative treatment method and system for waste incineration fly ash and silicon-rich waste Download PDFInfo
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- 239000010881 fly ash Substances 0.000 title claims abstract description 148
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- 238000004056 waste incineration Methods 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000011282 treatment Methods 0.000 title claims abstract description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 45
- 239000010703 silicon Substances 0.000 title claims abstract description 45
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- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 38
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000047 product Substances 0.000 claims abstract description 33
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- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000537371 Fraxinus caroliniana Species 0.000 description 1
- 235000010891 Ptelea trifoliata Nutrition 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
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- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/10—Burned or pyrolised refuse
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/30—Mixed waste; Waste of undefined composition
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Engineering & Computer Science (AREA)
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- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method and a system for cooperatively treating waste incineration fly ash and silicon-rich waste, wherein the method comprises the following steps: firstly, carrying out multistage water washing pretreatment on the waste incineration fly ash, mixing the wet fly ash slag with an alkaline preparation solution and silicon-rich waste, carrying out hydrothermal reaction, carrying out solid-liquid separation on hydrothermal product slurry, and carrying out desalination concentration on hydrothermal filtrate for reflux utilization; uniformly mixing the hydrothermal product filter cake with a washing liquid, introducing carbon dioxide gas into the mixed slurry, and carrying out solid-liquid separation on the washing slurry to obtain wet slag of the hydrated calcium silicate board, wherein the washing filtrate is recycled; and finally, uniformly mixing wet slag of the hydrated calcium silicate board with cement, fiber and organosilicon waterproofing agent, pressing for molding, and drying the obtained molded blank to prepare the calcium silicate board. The method realizes the targets of zero emission and zero pollution by a comprehensive treatment mode of 'multistage water washing + hydrothermal reaction under alkaline condition + calcium silicate board preparation + waste liquid circulation disposal'.
Description
Technical Field
The invention relates to the technical field of disposal of waste incineration fly ash, in particular to a cooperative treatment method and system of waste incineration fly ash and silicon-rich waste.
Background
Currently, the improvement of urban living standard brings about the increasing yield of urban garbage. Among the garbage disposal methods, the garbage incineration technology has the advantages of high-temperature sterilization, waste heat utilization and resource utilization, and becomes a main stream method for harmless garbage disposal. However, refuse incineration also presents problems of smoke and solid waste gas pollution. Fly ash is a part of solid waste, has a porous structure, has large specific surface area, and heavy metals and dioxin in the fly ash can enter soil and water through a percolation process and further be transferred and accumulated through a food chain, so that the fly ash seriously endangers human health.
Common harmless disposal modes of the waste incineration fly ash include high-temperature sintering, cementing, melting vitrification and other technologies. These innocuous treatment techniques belong to the conventional heat treatment techniques, but the treatment techniques are very costly. In recent years, the hydrothermal synergistic treatment of waste incineration fly ash has received a relatively wide attention. The hydrothermal method can not only enable dioxin to form small molecular organic matters through thermal decomposition and effectively reduce the content of the dioxin in fly ash, but also can generally obtain some aluminosilicate minerals with stable structures, so that the leaching concentration of heavy metals in the product is lower than the standard limit value. Meanwhile, the method has the advantages of simplicity in operation, low energy consumption, low equipment cost and the like, so that the hydrothermal method has certain advantages in the field of large-scale treatment of the fly ash.
However, at present, the technology for cooperatively treating the waste incineration fly ash by using water and heat still has a plurality of problems to be solved, and the problems are specifically expressed in:
1) Due to the high chlorine content in the waste incineration fly ash, dechlorination reaction in the hydrothermal degradation process of dioxin can be inhibited.
2) In order to enable the removal rate of dioxin in the waste incineration fly ash to reach a certain standard by the hydrothermal synergistic treatment, the reaction temperature of the hydrothermal treatment needs to be increased. However, the high temperature increases the energy consumption of the hydrothermal process, thereby reducing the economics of the hydrothermal treatment of fly ash.
3) Although dioxin is degraded in the process of hydrothermally synergistic treatment of fly ash, and the leaching rate of heavy metals is reduced at the same time, a large amount of waste liquid is discharged in the synergistic treatment process, and the steps comprise water washing pretreatment, hydrothermal reaction, product washing and the like. These links not only waste water resources, but also cause a great deal of pollution to the environment if the waste liquid is not treated.
4) A great advantage of the hydrothermal synergistic treatment of the waste incineration fly ash is that the produced aluminosilicate minerals can be applied to the fields of adsorption, catalysis, construction and the like. However, the recycling degree of the whole treatment system of the waste incineration fly ash is still low at present, and a complete system is not formed.
Disclosure of Invention
The invention provides a cooperative treatment method and a cooperative treatment system for waste incineration fly ash and silicon-rich waste, which are used for solving the defects of poor dechlorination effect, water resource waste and low resource utilization degree in the prior art and realizing harmless treatment and resource utilization of the waste incineration fly ash.
The invention provides a cooperative treatment method of waste incineration fly ash and silicon-rich waste, which comprises the following steps:
step S100, carrying out multistage washing pretreatment on the waste incineration fly ash to obtain wet fly ash and washing waste liquid;
step 200, mixing the wet fly ash slag with an alkaline preparation solution and silicon-rich waste, and performing hydrothermal reaction to obtain hydrothermal product slurry;
s300, carrying out solid-liquid separation on the hydrothermal product slurry to obtain a hydrothermal filtrate and a hydrothermal product filter cake, and carrying out desalination and concentration on the hydrothermal filtrate and then refluxing the hydrothermal filtrate into the alkaline preparation solution;
step S400, uniformly mixing the hydrothermal product filter cake with a washing liquid, and simultaneously introducing carbon dioxide gas into the mixed slurry to obtain a washing slurry;
s500, carrying out solid-liquid separation on the washing slurry to obtain washing filtrate and wet residues of hydrated calcium silicate plates, wherein the washing filtrate flows back into the washing liquid;
And S600, uniformly mixing the wet slag of the hydrated calcium silicate board with cement, fiber and organosilicon waterproofing agent, pressing for molding, and drying the obtained molded blank to prepare the calcium silicate board.
According to the method for cooperatively treating the waste incineration fly ash and the silicon-rich waste provided by the invention, in the step S100, the multistage water washing pretreatment is performed in a plurality of water washing units connected in series, and the method further comprises the following steps:
step S110, uniformly mixing the waste incineration fly ash with water washing water to obtain fly ash slurry;
s120, carrying out solid-liquid separation on the fly ash slurry to obtain a solid phase material;
s130, introducing water washing water to perform displacement washing on the solid phase material to obtain fly ash filter residues and water washing filtrate;
and step 140, enabling the fly ash filter residues to enter a next-stage washing unit, and repeating the steps 110-130.
According to the cooperative treatment method of the waste incineration fly ash and the silicon-rich waste, the water washing filtrate reversely flows back to the upper water washing unit, one part of the water washing filtrate is used for being mixed with the waste incineration fly ash or the fly ash filter residues to form fly ash slurry, and the other part of the water washing filtrate is used for displacement washing.
According to the method for cooperatively treating the waste incineration fly ash and the silicon-rich waste, the step S100 further comprises the cyclic treatment of the washing waste liquid, and the cyclic treatment of the washing waste liquid further comprises the following steps:
Step S150, removing and purifying calcium ions and heavy metal ions from the washing waste liquid to obtain a purified liquid;
and step 160, evaporating and desalting the purified liquid to obtain chloride salt crystals and desalted water, and refluxing the desalted water to the washing unit for recycling.
According to the method for co-processing waste incineration fly ash and silicon-rich waste provided by the invention, in the step S300, the concentration processing of the hydrothermal filtrate further comprises:
introducing waste heat exhaust steam of a waste incineration power plant to heat the hydrothermal filtrate so as to realize evaporation concentration until the concentration of the hydrothermal filtrate is greater than or equal to a preset concentration;
cooling the hydrothermal filtrate, and performing solid-liquid separation to obtain concentrated alkali liquor and chloride salt crystals, wherein the concentrated alkali liquor flows back into the alkaline preparation solution.
According to the method for cooperatively treating the waste incineration fly ash and the silicon-rich waste, in the step S500, when the reflux times of the washing filtrate reach the preset cycle times, the washing filtrate is added into the hydrothermal filtrate in a reflux manner so as to realize the evaporative crystallization of the washing filtrate, and carbonate crystals are obtained.
According to the method for cooperatively treating the waste incineration fly ash and the silicon-rich waste, in the step S400, carbon dioxide gas is introduced into the mixed slurry to adjust the pH value to 9.0-9.2.
The invention also provides a cooperative treatment system of the waste incineration fly ash and the silicon-rich waste, which comprises a water washing pretreatment subsystem, a hydrothermal treatment subsystem, a hydrothermal waste liquid circulation subsystem and a calcium silicate board preparation subsystem;
the washing pretreatment subsystem comprises a first feeding device, a plurality of washing units and a first discharging device which are sequentially communicated, wherein each washing unit comprises a washing device and a filtering device which are connected; the first feeding device is used for receiving the waste incineration fly ash to be treated;
the hydrothermal treatment subsystem comprises a second feeding device, an alkali liquor configuration tank, a carbon dioxide gas storage tank, a hydrothermal reactor, a first solid-liquid separation device, a washing device, a second solid-liquid separation device and a second discharging device which are sequentially communicated; the second feeding device is used for receiving silicon-rich waste, and three material inlets of the hydrothermal reactor are respectively connected with a discharge hole of the first discharging device, a discharge hole of the second feeding device and a liquid outlet of the alkali liquor configuration tank; the gas outlet of the carbon dioxide gas storage tank is connected with the gas inlet of the washing device, and the filtrate outlet of the second solid-liquid separation device is connected with the washing liquid inlet of the washing device;
The hydrothermal waste liquid circulation subsystem comprises an alkali liquor evaporation device and an alkali liquor filtering tank which are sequentially communicated; the filtrate outlet of the first solid-liquid separation device is connected with the feed inlet of the alkali liquor evaporation device, and the filtrate outlet of the alkali liquor filter tank is connected with the feed inlet of the alkali liquor configuration tank;
the calcium silicate board preparation subsystem comprises a third feeding device, a fourth feeding device, a fifth feeding device, a stirring device, a pressing die device and a drying device which are sequentially communicated; the third feeding device is used for receiving cement, the fourth feeding device is used for receiving fibers, and the fifth feeding device is used for receiving organosilicon waterproofing agent; four material inlets of the stirring device are respectively connected with the discharge port of the second discharging device, the discharge port of the third feeding device, the discharge port of the fourth feeding device and the discharge port of the fifth feeding device.
According to the collaborative treatment system for the waste incineration fly ash and the silicon-rich waste, each level of the water washing unit further comprises a replacement water tank connected with the filtering device, the water inlet of the water washing device of the last level and the water inlet of the replacement water tank are used for receiving initial water washing, and the water inlets of the water washing devices of other levels and the water inlet of the replacement water tank are connected with the filtrate outlet of the filtering device of the subsequent level so as to recycle the water washing water discharged by the filtering device of the subsequent level.
The invention provides a collaborative treatment system for waste incineration fly ash and silicon-rich waste, which further comprises a washing waste liquid circulation subsystem, wherein the washing waste liquid circulation subsystem comprises a reaction sedimentation tank and an evaporation crystallization device which are sequentially communicated, a liquid inlet of the reaction sedimentation tank is connected with a filtrate outlet of a first-stage filtering device, and a condensate outlet of the evaporation crystallization device is connected with the washing liquid circulation tank.
According to the collaborative treatment method and the collaborative treatment system for the waste incineration fly ash and the silicon-rich waste, firstly, the waste incineration fly ash is subjected to multistage water washing pretreatment, so that chloride salt and part of soluble heavy metals in the waste incineration fly ash can be reduced, the decomposition rate of dioxin in the hydrothermal reaction is further improved, and the aim of efficiently degrading the dioxin is fulfilled; then, an alkaline configuration solution is used in the hydrothermal reaction, so that the high temperature required by the hydrothermal reaction is reduced to a certain extent, the energy consumption of a hydrothermal method is reduced, the removal rate of dioxin is improved, and the hydrothermal synergistic high-efficiency treatment of the waste incineration fly ash is realized; meanwhile, the silicon-rich waste is used in the hydrothermal reaction, so that the cost of a silicon source is reduced, and the purposes of harmlessness and recycling of various dangerous wastes are realized; then, when washing and dealkalizing the filter cake of the hydrothermal product, a mode of introducing carbon dioxide gas is adopted to promote the removal of soluble alkali, optimize the dealkalization performance, improve the removal rate of the soluble alkali in the washing and dealkalization step, and simultaneously increase the recycling times of the washing liquid; the waste liquid in the links of hydrothermal reaction, product washing and the like is subjected to cleaning treatment and waste liquid circulation, so that the recycling of the waste water is realized, the contradiction between supply and demand of water resources can be relieved, and the water environment pollution is reduced; finally, tobermorite is generated through hydrothermal method, and a high-value building material calcium silicate board is further produced, so that the resource utilization of the waste incineration fly ash is realized, and the integral treatment system of the waste incineration fly ash with higher economic benefit, resource utilization and system completeness is formed.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for cooperatively treating waste incineration fly ash and silicon-rich waste;
FIG. 2 is a schematic flow chart of the multi-stage water-washing pretreatment method provided by the invention;
FIG. 3 is a schematic flow chart of the method for circularly treating the hydrothermal waste liquid;
FIG. 4 is a scanning electron microscope image of a hydrothermal product produced by an embodiment of the invention.
Description of the embodiments
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The terms "first", "second" in the embodiments of the present application are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the terms "comprise" and "have," along with any variations thereof, are intended to cover non-exclusive inclusions. For example, a system, article, or apparatus that comprises a list of elements is not limited to only those elements or units listed but may alternatively include other elements not listed or inherent to such article, or apparatus. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
As shown in fig. 1, the method for cooperatively treating the waste incineration fly ash and the silicon-rich waste provided by the embodiment of the invention comprises the following steps:
and step S100, performing multistage washing pretreatment on the waste incineration fly ash to obtain wet fly ash and washing waste liquid.
The chlorine salt content in the waste incineration fly ash is reduced by adopting a multi-stage water washing pretreatment mode. Specifically, the waste incineration fly ash and the water washing water are fully mixed and uniformly stirred according to the proportion of 8-15 mL/g at normal temperature, so that chloride ions in the fly ash are fully leached into the water. In a specific embodiment, the ratio of waste incineration fly ash to wash water may be 10mL/g. And then carrying out solid-liquid separation on the obtained fly ash slurry, continuously repeating the steps of water washing and solid-liquid separation on the obtained solid-phase material, wherein the repetition time can be determined according to the chloride salt content of the waste incineration fly ash, and the ideal chloride salt removal rate can be obtained by repeating the water washing for three times. The content of soluble chloride in the waste incineration fly ash after the multilevel water washing pretreatment is not more than 2%, and the chloride removal rate is more than 90%.
And step 200, mixing the wet fly ash slag with an alkaline preparation solution and silicon-rich waste, and performing hydrothermal reaction to obtain hydrothermal product slurry.
This step is used to provide hydrothermal reaction conditions of appropriate temperature, pressure to reduce the dioxin content in the fly ash and fix the heavy metals therein. Specifically, firstly, adding a sodium hydroxide solution with the concentration higher than that of hydrothermal solution alkali and industrial clear water into an alkali solution preparation tank according to a certain proportion, uniformly stirring and preparing the sodium hydroxide solution with the concentration of 0.3-0.5 mol/L for introducing the sodium hydroxide solution into a hydrothermal reactor for reaction. In a specific embodiment, the concentration of the alkaline configuration solution is 0.5mol/L. The alkaline preparation solution is added in the hydrothermal reaction, so that the high temperature required by the hydrothermal reaction is reduced to a certain extent, the energy consumption of a hydrothermal method is reduced, the removal rate of dioxin is improved, and the hydrothermal synergistic efficient treatment of the waste incineration fly ash is realized.
The silicon-rich waste in this embodiment refers to industrial waste products with high silicon content, such as coal fly ash or sludge, which can be directly added into the hydrothermal reactor, while the sludge needs to be dehydrated and then added into the hydrothermal reactor. Particularly, the waste incineration fly ash and the heavy metal sludge are subjected to hydrothermal treatment, so that the method is a method for cooperatively disposing various dangerous wastes, can solve the problem of slightly high cost caused by using silicon sources such as coal-fired fly ash, kaolin and the like, and can realize the purposes of harmlessness and recycling of various dangerous wastes.
The addition ratio of the wet fly ash slag to the silicon-rich waste is required to meet the requirement that the silicon-calcium ratio is 1:1, and then the alkaline preparation solution is added according to the solid-liquid ratio of 8-15 mL/g for full mixing and uniform stirring. The temperature of the hydrothermal reaction is 150-300 ℃, the reaction pressure is 4-6 MPa, the reaction time is 6-12 h, and the reaction stirring speed is 200-400 rpm. In a specific example, the wet slag of the fly ash and the fly ash of the fire coal are mixed according to the mass ratio of 3:7, and 0.5mol/L alkaline preparation solution is added according to the solid-to-liquid ratio of 10mL/g, the reaction condition of the hydrothermal reactor is set to 150 ℃, 5MPa, the reaction time is 12h, and the reaction stirring speed is 300rpm.
TABLE 1 leaching rates of heavy metals in refuse incineration fly ash, coal-fired fly ash and 30% hydrothermal samples
| Units: % of (B) | |||||
| Sample of | Cr | Cu | Ni | Pb | Zn |
| Fly ash from refuse incineration | 10.99 | 27.61 | 12.85 | 7.44 | 28.34 |
| Coal-fired fly ash | 35.00 | 15.97 | 10.03 | 2.05 | 7.26 |
| 30% hydrothermal sample | 6.19 | 16.97 | 11.38 | 3.37 | 21.35 |
Fig. 4 shows a scanning electron microscope image of a hydrothermal product produced by the embodiment of the invention, and as can be seen from table 1 and fig. 4, the leaching rate of heavy metal elements of the hydrothermal product is lower than that of an untreated sample, which indicates that heavy metals remained in the final hydrothermal product are better stabilized, and the purpose of harmless fly ash is achieved.
And S300, carrying out solid-liquid separation on the hydrothermal product slurry to obtain a hydrothermal filtrate and a hydrothermal product filter cake, and carrying out desalination and concentration on the hydrothermal filtrate and then refluxing the hydrothermal filtrate into an alkaline preparation solution.
The step carries out desalination and concentration on the hydrothermal filtrate for recycling, thereby saving water resources and reducing the dosage of alkaline medicament. Specifically, the method can be used for treating the hydrothermal waste liquid in an evaporation concentration mode, the heating steam can be used for taking waste heat exhaust steam of a power plant as a high-temperature heat exchange source, and heat sources in other ways can also be utilized.
And step S400, uniformly mixing the hydrothermal product filter cake with the washing liquid, and simultaneously introducing carbon dioxide gas into the mixed slurry to obtain washing slurry.
This step is used to elute the lye retained on the filter cake of the hydrothermal product. Specifically, the mass ratio of the hydrothermal product filter cake to the washing liquid is (1-5): 10, the initial washing liquid can be industrial clear water, the hydrothermal product filter cake and the washing liquid are fully and uniformly stirred, and carbon dioxide gas is introduced into the mixed slurry until the pH value of the mixed slurry reaches 9.0-9.2. By CO 2 The acid gas is dissolved in water to promote the removal of soluble alkali, so that the removal rate of the soluble alkali in the water-wash alkali removal step is improved, the water-wash alkali removal effect is enhanced, the water consumed for adjusting the pH value in the subsequent washing waste liquid recycling process can be saved, and meanwhile, if the introduced acid gas is waste incineration or CO-rich in kiln waste gas treatment and the like, the acid gas is added into the waste liquid 2 The gas also accords with the recycling economy concept of treating waste with waste.
And S500, performing solid-liquid separation on the washing slurry to obtain washing filtrate and wet residues of the hydrated calcium silicate plates, and refluxing the washing filtrate into the washing liquid.
Because carbon dioxide gas is introduced in the step S400, the washed filtrate can be directly recycled, and the recycling times are more than or equal to 5 times and less than or equal to 100 times.
And S600, uniformly mixing wet slag of the hydrated calcium silicate board with cement, fiber and organosilicon waterproofing agent, pressing for molding, and drying the obtained molded blank to prepare the calcium silicate board.
The step is used for preparing the hydrophobic fiber reinforced calcium silicate board from the treated hydrothermal product, namely the wet slag of the hydrated calcium silicate board, so as to realize harmless and resource utilization of the fly ash. Specifically, the cement can be ordinary silicate cement, the fiber can be cotton fiber or paper pulp fiber, and the addition ratio of wet slag of the hydrated calcium silicate board to the cement is 60-90 wt% and 5-25 wt% and 5-15 wt% of the fiber. The organosilicon waterproofing agent is one or a mixture of more than two of isobutyl trimethoxy silane, isobutyl triethoxy silane, isooctyl triethoxy silane and propyl triethoxy silane, and the addition amount is 1-5wt%.
In a specific embodiment, the wet slag of the hydrated calcium silicate board, cement and fiber are put into a stirring device according to the mass ratio of 60:25:15 for fully stirring and mixing, and an organosilicon waterproofing agent is added to prepare a semi-finished product of the calcium silicate board; and then putting the mixed semi-finished product of the calcium silicate board into a die device, pressing and forming the semi-finished product of the calcium silicate board under the pressure of 45 MPa, and further sending the semi-finished product of the calcium silicate board into a vacuum drying oven to be dried for 12 hours at the temperature of 80 ℃ to prepare the non-autoclaved hydrophobic fiber reinforced calcium silicate board.
The method for cooperatively treating the waste incineration fly ash and the silicon-rich waste provided by the embodiment aims at carrying out post-treatment on a large amount of domestic waste incineration fly ash at present, realizes harmless and recycling of the fly ash, has the advantages of high efficiency, cleanliness and low carbon, and has the following specific technical characteristics:
(1) The chlorine salt and part of soluble heavy metals in the waste incineration fly ash are reduced by adopting multistage water washing pretreatment, so that the decomposition rate of dioxin in the hydrothermal reaction is further improved, and the purpose of efficiently degrading the dioxin is achieved.
(2) The alkaline additive is added in the hydrothermal reaction, so that the high temperature required by the hydrothermal reaction is reduced to a certain extent, the energy consumption of a hydrothermal method is reduced, the removal rate of dioxin is improved, and the hydrothermal synergistic efficient treatment of the waste incineration fly ash is realized.
(3) The silicon-rich waste is used for replacing the conventional silicon source in the hydrothermal reaction, so that the cost of the silicon source is reduced, and the heavy metal sludge and the waste incineration fly ash are subjected to the synergistic hydrothermal treatment, so that the purposes of harmlessness and recycling of various dangerous wastes are realized.
(4) CO can be introduced when the hydrothermal filter cake is subjected to water alkali elution 2 The dealkalization performance in the water washing process is optimized by a gas mode, and CO is utilized 2 The dissolution of the acid gas into water can promote the removal of soluble alkali, improve the removal rate of soluble alkali in the step of water washing alkali, save water consumed by adjusting the pH value in the subsequent cyclic utilization process, and simultaneously, if the introduced acid gas is CO-rich for treating kiln waste gas and the like 2 The gas accords with the recycling economy concept of treating waste with waste.
(5) The method has the advantages that the waste liquid in the links of water washing pretreatment, hydrothermal reaction, product washing and the like is subjected to cleaning treatment and waste liquid circulation, the resource utilization of the waste water is realized, and the method has important significance for relieving contradiction between water resource supply and demand and reducing water environment pollution in China.
(6) The tobermorite is generated through hydrothermal process, and the high-value building material calcium silicate board is further produced, so that the resource utilization of the waste incineration fly ash is realized, and the integral treatment system of the waste incineration fly ash with higher economic benefit, resource utilization and system completeness is formed.
Further, in step S100, the multi-stage water washing pretreatment is performed in a plurality of water washing units connected in series, further comprising:
and step S110, uniformly mixing the waste incineration fly ash with water washing water to obtain fly ash slurry.
And step S120, performing solid-liquid separation on the fly ash slurry to obtain a solid-phase material.
S130, introducing water washing water to perform displacement washing on the solid-phase materials to obtain fly ash filter residues and water washing filtrate; the water washing filtrate reversely flows back to the upper water washing unit, one part is used for mixing with the waste incineration fly ash or the fly ash filter residues to form fly ash slurry, and the other part is used for displacement washing.
And step S140, enabling the fly ash filter residues to enter a next-stage washing unit, and repeating the steps S110-S130.
As shown in fig. 2, this embodiment is described by taking three-stage water-washing pretreatment as an example. Specifically, the water washing pretreatment system adopts three-stage water washing units, and each stage of water washing unit comprises a water washing device (such as a water washing tank with a stirring function), a filtering device (such as a vacuum filter tank) and a replacement water tank. The water washing device is used for uniformly mixing the waste incineration fly ash or the solid-phase material of the upper stage with water washing water; the filter device is used for filtering the fly ash slurry, and carrying out displacement washing on the filter cake after the filtration is completed; the displacement water tank is used for storing the water washing water required by displacement washing. In order to facilitate the transportation of the solid phase materials, a filter cake crusher can be also arranged.
The water washing device and the water washing water in the replacement water tank can be all taken from industrial clean water, water resources are saved, and the water washing device and the water washing water in the replacement water tank can be circulated among all levels of water washing units, most of chloride ions can be washed away in the first level water washing process, so that the water washing filtrate of the second level and the third level can be recycled, the circulation mode can be forward or reverse, the description is given by taking reverse circulation as an example in the embodiment, and the water washing water in the water washing device and the water washing water in the replacement water tank can be sourced from the water washing filtrate of the next level.
The whole water washing pretreatment flow is as follows: firstly, the fly ash feeding pipeline and the water washing pipeline are utilized to introduce the waste incineration fly ash and the industrial clean water, the first-stage water washing tank is connected with the fly ash hopper through a feeding pipe, and the fly ash feeding pipe is provided with a spiral conveying device (or other commonly used powder conveying devices) for conveying fly ash solid powder. Fully mixing the waste incineration fly ash and water in a water washing tank according to the proportion of 8-15 mL/g, and uniformly stirring to fully leach chloride ions in the fly ash.
In each stage of washing unit, the washing tank is communicated with the filter tank through a pipeline, and the filter tank is subjected to solid-liquid separation twice, wherein the solid-liquid separation is performed on the water ash mixture introduced into the washing tank, and the replacement washing is performed on the clean water introduced from the replacement water tank and having the ratio of 1mL/g with the fly ash. It should be noted that in the suction filtration process, it is necessary to ensure that the water level of the replacement water tank is higher than a fixed value, and the fixed value is equal to the equivalent volume of water of fly ash; when the water level of the replacement water tank is lower than the value, the equivalent amount of water of fly ash is added, and the water quantity is always enough during replacement washing. After solid-liquid separation, the filter cake enters a crusher for crushing treatment, and the feeding pipeline of each stage of crusher is connected with a water washing tank of the next stage so as to send the filter cake into the water washing device of the next stage for multiple water washing. And part of filtrate obtained after the solid-liquid separation of the second-stage and third-stage filter tanks is directly sent to a waste liquid treatment process, and the remaining filtrate flows back to the previous stage through a countercurrent pipeline until the filtrate is filtered by the first-stage water washing device and then is introduced into the waste liquid treatment process through the pipeline for treatment.
The water washing is added to perform displacement washing (namely, the surface of the filter cake is washed by water and substances in the filter cake are displaced and transferred through the filter cake) in the suction filtration process of the multistage water washing process, so that the same chlorine removal rate is achieved, the water washing times of the multistage water washing are reduced, the water demand in the pretreatment process is greatly reduced, the water washing cost is reduced, and the method is worthy of industrial application.
Still further, step S100 further includes a washing waste liquid circulation process, which further includes:
and step S150, removing and purifying calcium ions and heavy metal ions from the washing waste liquid to obtain a purified liquid.
And step 160, evaporating and desalting the purified liquid to obtain chloride salt crystals and desalted water, and refluxing the desalted water to the water washing unit for recycling.
Specifically, firstly, filtrate flowing out of a filtering device is introduced into a sedimentation tank for separating calcium ions and heavy metal ions, and the specific mode is that a heavy metal capturing agent (sodium sulfide, sodium thiosulfate and the like) and sodium carbonate (sodium carbonate ratio waste liquid is 0.016-0.02 g/L) are added into the sedimentation tank, and solid-liquid separation is carried out after heavy metal and calcium carbonate are settled. And then evaporating and desalting the separated filtrate to obtain chloride salt crystals and condensed water, and conveying the condensed water into a washing liquid circulating pool, conveying the condensed water into a clear water pipeline through a pump, and finally, circularly utilizing the condensed water in a washing tank and a replacement water tank. The evaporation desalting process can adopt a falling film evaporation crystallization tower, heat required by evaporation can be sourced from heat sources which can also utilize other ways, the embodiment considers realizing self-production and self-sales of fly ash, and waste heat exhaust steam of a waste incineration power plant is preferentially used.
Further, as shown in fig. 3, in step S300, the concentration process of the hydrothermal filtrate further includes:
waste heat exhaust steam of a waste incineration power plant is introduced to heat the hydrothermal filtrate so as to realize evaporation concentration until the concentration of the hydrothermal filtrate is greater than or equal to a preset concentration; cooling the hydrothermal filtrate, and performing solid-liquid separation to obtain concentrated alkali liquor and chloride salt crystals, wherein the concentrated alkali liquor is refluxed into an alkaline preparation solution.
In the hydrothermal reaction process, if the hydrothermal alkali liquor is recycled for a plurality of times, alkali concentration is reduced along with the loss of the hydrothermal solid product, meanwhile, chloride in the fly ash can be enriched in the recycled alkali liquor in the plurality of times of use, and when the chloride is enriched to a certain degree, the crystal growth in the hydrothermal process can be influenced. To solve the above problems, the pressure dependence on the boiling point of the liquid can be used to remove the corresponding chloride impurities in the recycle line.
Specifically, the hydrothermal filtrate is pumped to an alkali liquor evaporation tank, waste alkali liquor in the alkali liquor evaporation tank is heated by utilizing waste heat exhaust gas of a waste incineration power plant, the generated secondary steam is condensed into condensed water through a heat exchanger, non-condensable gas is pumped out through a vacuum pump, the pressure in the evaporation tank is reduced to (-0.06 to-0.08 MPa), so that the boiling point of the hydrothermal filtrate is reduced, and the hydrothermal filtrate is evaporated and concentrated. When the hydrothermal filtrate is evaporated and concentrated to a specified concentration, namely, the concentration of the alkali liquor required by the hydrothermal reaction (for example, 0.5 mol/L) is higher than or equal to the pH value of the alkali liquor required by the hydrothermal reaction, cooling the alkali liquor in the evaporation tank by using cooling circulating water, and obtaining chlorine salt crystals and concentrated alkali liquor after the temperature of the alkali liquor is reduced to a set temperature (for example, 30 ℃). Filtering and separating the concentrated alkali liquor by an alkali liquor filter tank, separating chlorine salts such as sodium chloride and the like to obtain the concentrated alkali liquor, refluxing the concentrated alkali liquor into an alkali liquor preparation tank, and sending the concentrated alkali liquor into a hydrothermal reactor according to the solid-to-liquid ratio requirement of the hydrothermal reaction to finish the recycling of the waste liquor.
Further, as shown in fig. 1 and 3, in step S500, when the number of times of reflux of the washing filtrate reaches a preset number of times of circulation, the washing filtrate is added back to the hydrothermal filtrate to effect evaporative crystallization of the washing filtrate, thereby obtaining carbonate crystals. The preset cycle number is greater than or equal to 5 times and less than or equal to 100 times, and the specific number can be set according to requirements. After the preset circulation times are reached, the waste liquid after washing and dealkalization is added into the evaporation circulation process of the hydrothermal filtrate through the corresponding pipelines in a reflux way, carbonate is separated after evaporation, and the separated filtrate is circulated along with the concentrated alkali liquor to be used as an alkaline preparation solution to enter an alkali liquor preparation tank.
As shown in fig. 1, the embodiment of the invention also provides a co-processing system for the waste incineration fly ash and the silicon-rich waste, which comprises a water washing pretreatment subsystem, a hydrothermal treatment subsystem, a hydrothermal waste liquid circulation subsystem and a calcium silicate board preparation subsystem. The water washing pretreatment subsystem is used for carrying out dechlorination water washing pretreatment on the transported garbage incineration fly ash, and the requirement of the chlorine removal rate of more than 90% is met. The hydrothermal treatment subsystem is used for carrying out hydrothermal reaction on the garbage incineration fly ash filter cake after the water washing pretreatment and the coal fly ash under the hydrothermal reaction condition of proper temperature and pressure, so that the content of dioxin in the fly ash is reduced, the stability of heavy metals in the fly ash is realized, and the harmless treatment of the fly ash is realized. The hydrothermal waste liquid circulation subsystem is used for treating various waste liquids generated in the hydrothermal treatment subsystem and recycling the waste liquids, so that the comprehensive utilization rate of the waste liquids in the system is improved. The calcium silicate board preparation subsystem is used for producing the tobermorite generated by the hydrothermal reaction, and the hydrophobic fiber reinforced calcium silicate board is produced by further processing, so that the resource utilization of the fly ash is realized.
The water washing pretreatment subsystem comprises a first feeding device, a plurality of water washing units connected in series and a first discharging device which are sequentially communicated. The first feeding device is used for receiving the waste incineration fly ash to be treated, and can be screw conveying equipment or other common powder conveying equipment, and is connected with the fly ash hopper through a feeding pipe and used for conveying solid powder of the waste incineration fly ash. The number of the washing units is two or more, and three washing units are taken as an example in this embodiment. Each stage of washing unit comprises a washing device and a filtering device which are connected, wherein the washing device is used for uniformly mixing the waste incineration fly ash or the solid-phase material of the previous stage with washing water, and a washing tank with a stirring function can be adopted; the filtering device is used for filtering the fly ash slurry, and after the filtering is completed, the filter cake is subjected to displacement washing, and a suction filtration or centrifugation mode can be adopted, such as a vacuum filter tank, a vacuum filter and the like. The first discharging device is used for conveying the wet slag of the fly ash obtained by the last stage of filtering device to the hydrothermal treatment subsystem to participate in the hydrothermal reaction, and a filter cake crusher can be adopted. In order to facilitate the transportation of solid phase materials, a filter cake crusher can be arranged between the washing units at all levels.
Each stage of the water washing unit also comprises a replacement water tank connected with the filtering device, and the replacement water tank is used for storing water washing water required by replacement washing. The water inlet of the water washing device of the last stage and the water inlet of the replacement water tank are used for receiving the initial water washing water, and the water inlets of the water washing devices of other stages and the water inlet of the replacement water tank are connected with the filtrate outlet of the filtering device of the later stage so as to recycle the water washing water discharged by the filtering device of the later stage.
The hydrothermal treatment subsystem comprises a second feeding device, an alkali liquor configuration tank, a carbon dioxide gas storage tank, a hydrothermal reactor, a first solid-liquid separation device, a washing device, a second solid-liquid separation device and a second discharging device which are sequentially communicated. The second feeding device is used for receiving silicon-rich waste, which can be screw conveying equipment or other common solid conveying equipment, and the silicon-rich waste comprises coal-fired fly ash or heavy metal sludge, municipal sludge or other sludge subjected to dehydration treatment. Three material inlets of the hydrothermal reactor are respectively connected with a discharge hole of the first discharging device and a discharge hole of the second feeding deviceThe port is connected with the liquid outlet of the alkali liquor preparation tank, and a stirring device is arranged in the hydrothermal reactor so as to uniformly mix the wet fly ash residue subjected to water washing pretreatment with the silicon-rich waste and the alkaline preparation solution, and meanwhile, the hydrothermal reactor can also provide a high-temperature and high-pressure environment so as to enable the mixed slurry to undergo a hydrothermal reaction, thereby synthesizing tobermorite. After the reaction is finished, the hydrothermal reactor is cooled to normal temperature, and the hydrothermal product and the hydrothermal liquid are subjected to solid-liquid separation by using a first solid-liquid separation device, wherein the first solid-liquid separation device can adopt a suction filtration or centrifugal mode, such as a vacuum suction filter. And then, the hydrothermal filtrate is sent into a hydrothermal waste liquid circulation subsystem, the filter cake of the hydrothermal product directly enters a washing device for dealkalization treatment, and the washing device can adopt a dealkalization tank with a stirring function. The washing device is also provided with an air inlet which is used for being connected with an air outlet of the carbon dioxide air storage tank, and the gas in the carbon dioxide air storage tank can be waste incineration waste gas after innocent treatment and is rich in CO 2 . After the hydrothermal product filter cake enters a washing device, adding industrial clean water according to the mass ratio of the hydrothermal product filter cake to water of (1-5): 10, fully stirring and washing, and introducing CO 2 Enhancing the alkali eluting effect of water. The washed mixed slurry enters a second solid-liquid separation device, solid-liquid separation is carried out on the washed tobermorite in a filter pressing dehydration mode, wet slag of the hydrated calcium silicate plate is obtained, and the second solid-liquid separation device can adopt a filter press to ensure water removal and shaping of the wet slag. The filtrate outlet of the second solid-liquid separation device is connected with the washing liquid inlet of the washing device so as to recycle the washing filtrate, and the washing filtrate is separated from the circulation and enters the hydrothermal liquid waste alkali evaporation tank for desalination treatment after a certain number of circulation.
As shown in fig. 3, the hydrothermal waste liquid circulation subsystem comprises an alkali liquor evaporation device and an alkali liquor filtering tank which are sequentially communicated. The filtrate outlet of the first solid-liquid separation device is connected with the feed inlet of the alkali liquor evaporation device so as to convey the hydrothermal filtrate into the alkali liquor evaporation device for evaporation concentration treatment. The filtrate outlet of the alkali liquor filter tank is connected with the liquid inlet of the alkali liquor preparation tank so as to carry out reflux recycling on the concentrated alkali liquor for filtering the chloride salt crystals. Specifically, the hydrothermal filtrate is pumped to an alkali liquor evaporation tank, waste alkali liquor in the alkali liquor evaporation tank is heated by utilizing waste heat exhaust gas of a waste incineration power plant, the generated secondary steam is condensed into condensed water through a heat exchanger, non-condensable gas is pumped out through a vacuum pump, the pressure in the evaporation tank is reduced to (-0.06 to-0.08 MPa), so that the boiling point of the hydrothermal filtrate is reduced, and the hydrothermal filtrate is evaporated and concentrated. When the hydrothermal filtrate is evaporated and concentrated to a specified concentration, namely, the concentration of the alkali liquor required by the hydrothermal reaction (for example, 0.5 mol/L) is higher than or equal to the pH value of the alkali liquor required by the hydrothermal reaction, cooling the alkali liquor in the evaporation tank by using cooling circulating water, and obtaining chlorine salt crystals and concentrated alkali liquor after the temperature of the alkali liquor is reduced to a set temperature (for example, 30 ℃). Filtering and separating the concentrated alkali liquor by an alkali liquor filter tank, separating chlorine salts such as sodium chloride and the like to obtain the concentrated alkali liquor, refluxing the concentrated alkali liquor into an alkali liquor preparation tank, and sending the concentrated alkali liquor into a hydrothermal reactor according to the solid-to-liquid ratio requirement of the hydrothermal reaction to finish the recycling of the waste liquor.
The calcium silicate board preparation subsystem comprises a third feeding device, a fourth feeding device, a fifth feeding device and a stirring device, a pressing die device and a drying device which are sequentially communicated. The third feeding device is used for receiving cement, the fourth feeding device is used for receiving fibers, and the fifth feeding device is used for receiving the organosilicon waterproofing agent. Four material inlets of the stirring device are respectively connected with a discharge hole of the second discharge device, a discharge hole of the third feed device, a discharge hole of the fourth feed device and a discharge hole of the fifth feed device so as to uniformly mix all materials to prepare a calcium silicate board semi-finished product, the mixed calcium silicate board semi-finished product is put into a compression molding device to be pressed and molded under the pressure of 45 MPa, and the mixture is further sent into a vacuum drying box to be dried under the condition of 80 ℃ for 12 h, so that the non-autoclaved hydrophobic fiber reinforced calcium silicate board is prepared.
Further, as shown in fig. 1, the co-processing system of the waste incineration fly ash and the silicon-rich waste further comprises a washing waste liquid circulation subsystem, wherein the washing waste liquid circulation subsystem comprises a reaction sedimentation tank and an evaporation crystallization device which are sequentially communicated, a liquid inlet of the reaction sedimentation tank is connected with a filtrate outlet of a first-stage filtering device, and a condensate outlet of the evaporation crystallization device is connected with the washing liquid circulation tank. Firstly, introducing filtrate flowing out of a filtering device into a reaction sedimentation tank for separating calcium ions and heavy metal ions, specifically, adding a heavy metal capturing agent (sodium sulfide, sodium thiosulfate and the like) and sodium carbonate (sodium carbonate ratio waste liquid is 0.016-0.02 g/L) into the reaction sedimentation tank, standing for solid-liquid separation after heavy metal and calcium carbonate are precipitated. And then evaporating and desalting the separated filtrate to obtain chloride salt crystals and condensed water, and conveying the condensed water into a washing liquid circulating pool, conveying the condensed water into a clear water pipeline through a pump, and finally, circularly utilizing the condensed water in a washing tank and a replacement water tank. The evaporation desalting process can adopt a falling film evaporation crystallization tower, heat required by evaporation can be sourced from heat sources which can also utilize other ways, the embodiment considers realizing self-production and self-sales of fly ash, and waste heat exhaust steam of a waste incineration power plant is preferentially used.
Compared with the prior art, the method and the system for the synergistic treatment of the waste incineration fly ash and the silicon-rich waste provided by the embodiment of the invention have the advantages that by adopting the comprehensive treatment mode of 'multistage water washing + hydrothermal reaction of alkaline condition + preparation of the calcium silicate board + recycling of waste liquid', the harmless treatments such as degradation of dioxin in the waste incineration fly ash and the coal fly ash and reduction of leaching rate of heavy metal are realized, and meanwhile, the high-value building material calcium silicate board is produced by utilizing the hydrothermal products after the harmless treatments of the waste incineration fly ash and the coal fly ash, so that the effective recycling utilization is realized, and the aim of zero emission of the water treatment process such as water washing and hydrothermal treatment in the recycling process of the fly ash is realized by recycling the waste liquid.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A synergistic treatment method of waste incineration fly ash and silicon-rich waste is characterized by comprising the following steps:
step S100, carrying out multistage washing pretreatment on the waste incineration fly ash to obtain wet fly ash and washing waste liquid;
step 200, mixing the wet fly ash slag with an alkaline preparation solution and silicon-rich waste, and performing hydrothermal reaction to obtain hydrothermal product slurry;
s300, carrying out solid-liquid separation on the hydrothermal product slurry to obtain a hydrothermal filtrate and a hydrothermal product filter cake, and carrying out desalination and concentration on the hydrothermal filtrate and then refluxing the hydrothermal filtrate into the alkaline preparation solution;
step S400, uniformly mixing the hydrothermal product filter cake with a washing liquid, and simultaneously introducing carbon dioxide gas into the mixed slurry to obtain a washing slurry;
s500, carrying out solid-liquid separation on the washing slurry to obtain washing filtrate and wet residues of hydrated calcium silicate plates, wherein the washing filtrate flows back into the washing liquid;
and S600, uniformly mixing the wet slag of the hydrated calcium silicate board with cement, fiber and organosilicon waterproofing agent, pressing for molding, and drying the obtained molded blank to prepare the calcium silicate board.
2. The method according to claim 1, wherein in step S100, the multi-stage water-washing pretreatment is performed in a plurality of water-washing units connected in series, further comprising:
Step S110, uniformly mixing the waste incineration fly ash with water washing water to obtain fly ash slurry;
s120, carrying out solid-liquid separation on the fly ash slurry to obtain a solid phase material;
s130, introducing water washing water to perform displacement washing on the solid phase material to obtain fly ash filter residues and water washing filtrate;
and step 140, enabling the fly ash filter residues to enter a next-stage washing unit, and repeating the steps 110-130.
3. The method according to claim 2, wherein the water washing filtrate is reversely returned to the upper stage water washing unit, and a part of the water washing filtrate is used for mixing with the waste incineration fly ash or the fly ash residue to form a fly ash slurry, and the other part is used for displacement washing.
4. The method according to claim 2, wherein the step S100 further comprises a water-washing waste liquid circulation treatment, the water-washing waste liquid circulation treatment further comprising:
step S150, removing and purifying calcium ions and heavy metal ions from the washing waste liquid to obtain a purified liquid;
and step 160, evaporating and desalting the purified liquid to obtain chloride salt crystals and desalted water, and refluxing the desalted water to the washing unit for recycling.
5. The method according to claim 1, wherein in the step S300, the concentration of the hydrothermal filtrate further comprises:
introducing waste heat exhaust steam of a waste incineration power plant to heat the hydrothermal filtrate so as to realize evaporation concentration until the concentration of the hydrothermal filtrate is greater than or equal to a preset concentration;
cooling the hydrothermal filtrate, and performing solid-liquid separation to obtain concentrated alkali liquor and chloride salt crystals, wherein the concentrated alkali liquor flows back into the alkaline preparation solution.
6. The method according to claim 5, wherein in step S500, when the number of times of reflux of the washing filtrate reaches a preset number of times of circulation, the washing filtrate is added back to the hydrothermal filtrate to effect evaporative crystallization of the washing filtrate, thereby obtaining carbonate crystals.
7. The method for collaborative treatment of waste incineration fly ash and silicon-rich waste according to claim 1, characterized in that in the step S400, carbon dioxide gas is introduced into the mixed slurry to adjust the pH to 9.0-9.2.
8. The cooperative treatment system for the waste incineration fly ash and the silicon-rich waste is characterized by comprising a water washing pretreatment subsystem, a hydrothermal treatment subsystem, a hydrothermal waste liquid circulation subsystem and a calcium silicate board preparation subsystem;
the washing pretreatment subsystem comprises a first feeding device, a plurality of washing units and a first discharging device which are sequentially communicated, wherein each washing unit comprises a washing device and a filtering device which are connected; the first feeding device is used for receiving the waste incineration fly ash to be treated;
the hydrothermal treatment subsystem comprises a second feeding device, an alkali liquor configuration tank, a carbon dioxide gas storage tank, a hydrothermal reactor, a first solid-liquid separation device, a washing device, a second solid-liquid separation device and a second discharging device which are sequentially communicated; the second feeding device is used for receiving silicon-rich waste, and three material inlets of the hydrothermal reactor are respectively connected with a discharge hole of the first discharging device, a discharge hole of the second feeding device and a liquid outlet of the alkali liquor configuration tank; the gas outlet of the carbon dioxide gas storage tank is connected with the gas inlet of the washing device, and the filtrate outlet of the second solid-liquid separation device is connected with the washing liquid inlet of the washing device;
The hydrothermal waste liquid circulation subsystem comprises an alkali liquor evaporation device and an alkali liquor filtering tank which are sequentially communicated; the filtrate outlet of the first solid-liquid separation device is connected with the feed inlet of the alkali liquor evaporation device, and the filtrate outlet of the alkali liquor filter tank is connected with the feed inlet of the alkali liquor configuration tank;
the calcium silicate board preparation subsystem comprises a third feeding device, a fourth feeding device, a fifth feeding device, a stirring device, a pressing die device and a drying device which are sequentially communicated; the third feeding device is used for receiving cement, the fourth feeding device is used for receiving fibers, and the fifth feeding device is used for receiving organosilicon waterproofing agent; four material inlets of the stirring device are respectively connected with the discharge port of the second discharging device, the discharge port of the third feeding device, the discharge port of the fourth feeding device and the discharge port of the fifth feeding device.
9. The co-processing system of waste incineration fly ash and silicon-rich waste according to claim 8, wherein each stage of the water washing unit further comprises a replacement water tank connected to the filtering device, the water inlet of the water washing device of the last stage and the water inlet of the replacement water tank are both used for receiving the initial water washing, and the water inlets of the water washing devices of the other stages and the water inlet of the replacement water tank are connected to the filtrate outlet of the filtering device of the subsequent stage so as to recycle the water washing water discharged from the filtering device of the subsequent stage.
10. The collaborative treatment system of waste incineration fly ash and silicon-rich waste according to claim 9, further comprising a washing waste liquid circulation subsystem, wherein the washing waste liquid circulation subsystem comprises a reaction sedimentation tank and an evaporation crystallization device which are sequentially communicated, a liquid inlet of the reaction sedimentation tank is connected with a filtrate outlet of a first-stage filtering device, and a condensate outlet of the evaporation crystallization device is connected with the washing liquid circulation tank.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117776652A (en) * | 2024-02-27 | 2024-03-29 | 吉奥固化(上海)新材料有限公司 | Cementing composition and cementing material |
| CN117798179A (en) * | 2024-02-28 | 2024-04-02 | 中蓝长化工程科技有限公司 | Resource utilization method of household garbage incineration fly ash |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117776652A (en) * | 2024-02-27 | 2024-03-29 | 吉奥固化(上海)新材料有限公司 | Cementing composition and cementing material |
| CN117776652B (en) * | 2024-02-27 | 2024-05-28 | 吉奥固化(上海)新材料有限公司 | Cementing composition and cementing material |
| CN117798179A (en) * | 2024-02-28 | 2024-04-02 | 中蓝长化工程科技有限公司 | Resource utilization method of household garbage incineration fly ash |
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