CN115228875A - Method for stabilizing and fixing dechlorinated fly ash - Google Patents
Method for stabilizing and fixing dechlorinated fly ash Download PDFInfo
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- CN115228875A CN115228875A CN202210638588.8A CN202210638588A CN115228875A CN 115228875 A CN115228875 A CN 115228875A CN 202210638588 A CN202210638588 A CN 202210638588A CN 115228875 A CN115228875 A CN 115228875A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
Abstract
The invention discloses a method for stabilizing and fixing dechlorinating fly ash, which comprises the steps of dechlorinating a fly ash raw material by using a fly ash dechlorinating device, collecting strong alkali liquor in a cathode chamber, collecting slurry of a metal precipitate and a fly ash area, and drying to obtain a solid precipitate; taking rice hulls, and carrying out anoxic pyrolysis to obtain rice hull ash; mixing the rice hull ash with strong alkali liquor, and carrying out water bath reaction to obtain sodium silicate slurry; and adding the solid precipitate into the sodium silicate slurry, performing hydrolysis reaction, and performing centrifugal filtration to obtain a stabilized solid. According to the method for stably immobilizing the dechlorinated fly ash, firstly, chlorine in the fly ash can be effectively removed, heavy metals are precipitated and separated out, secondary pollution caused by a washing method is reduced, and no secondary waste is generated; secondly, a new technology for fixing dechlorinated fly ash by utilizing the waste rice hulls generated in agricultural product processing is provided, waste is treated by waste, the cost is low, and the stabilization effect is good.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a method for stabilizing and fixing dechlorinating fly ash, which treats waste by waste and has low cost and good stabilizing effect.
Background
The cleaning amount of the municipal solid waste is 2.42 hundred million tons, the harmless rate reaches 99.2 percent, wherein the burning amount is about 1.22 hundred million tons, and accounts for 50.7 percent of the total harmless amount. The incineration technology can quickly realize volume reduction, volume reduction and harmlessness of the garbage, and can realize energy recovery, so the method can be quickly popularized.
The incineration fly ash is generated in the incineration process of municipal domestic waste, and organic matters in the waste are mainly discharged in the form of gaseous substances in the incineration process of the waste; the inorganic substances mainly form solid particles, wherein large-particle solids are deposited on the bottom of the incinerator and a fire grate and are called bottom ash, while fine particles float in the flue gas and enter a flue gas purification system along with the flue gas, the particles form 50% of incineration fly ash, the rest incineration fly ash is derived from limestone or active carbon added in the flue gas purification process, the limestone or active carbon and the active carbon are captured and collected in a dust collector (an electrostatic dust collector, a cloth bag dust collector and the like), meanwhile, a part of fine particles are settled down at the bottom of a flue and a chimney, and the captured and settled fine particles are called incineration fly ash.
The incineration fly ash has low water content, is light grey powder, has uneven fly ash particle size, complex structure and variable properties, exists in amorphous state and polycrystalline polymer structure forms, and generally has the fly ash particle size of less than 100 mu m, rough surface, larger specific surface and higher porosity. The chemical components of the incineration fly ash comprise Cl, ca, K, na, si, al, O and other elements, and the main chemical components are CaO, siO2, al2O3 and Fe2O3. In addition, incineration fly ash often contains high-concentration heavy metals such as Hg, pb, cd, cu, cr, zn and the like, and the heavy metals mainly exist in the forms of aerosol small particles and are enriched on the surfaces of fly ash particles; meanwhile, the incineration fly ash also contains a small amount of dioxin and furan, so the incineration fly ash has strong potential hazard.
According to the regulations of pollution control Standard on incineration of domestic garbage (GB 18485-2014): the household garbage incineration fly ash is managed according to dangerous waste. Therefore, the fly ash must be collected separately, and must not be mixed with household garbage, incineration residue, etc., and other hazardous wastes. At present, incineration fly ash is mainly treated by an immobilization technology or a stabilization technology and then enters a hazardous waste landfill for landfill treatment; or, the incineration fly ash is simply treated on site and then sent to a safe landfill site for safe landfill treatment, but the construction and operation costs of the safe landfill site are very high, which makes the waste incineration plant difficult to bear, so the use of the method is gradually reduced.
At present, methods capable of effectively disposing the garbage fly ash include chemical agent stabilization technology, high-temperature melting heat treatment technology and solidification/stabilization technology. The chemical agent stabilizing method is to convert heavy metal ions into water-insoluble macromolecular complexes or inorganic minerals by using chemical agents, but the heavy metal ions are in contact with acidic substances and then released.
The high-temperature heat treatment technology is to use equipment to cause a high-temperature environment, and can be matched with partial medicines at high temperature to realize the stable solidification of heavy metals in the garbage fly ash and the degradation of dioxin. But needs larger initial investment and continuous management operation investment, and has lower return rate. Secondary pollution is easily formed.
The solidification and stabilization technology is regarded as the most promising garbage fly ash disposal technology and is a common means for disposing the garbage fly ash internationally at present. The main curing/stabilizing mechanism is to form inert products by curing/stabilizing the easily leached heavy metal elements, or to fully wrap the heavy metal elements by forming inert substances. However, excessive chlorine in the fly ash can affect the immobilization reaction and also lead to the heavy metals in the fly ash to be leached out in large quantity.
Disclosure of Invention
The invention aims to provide a method for stabilizing and fixing dechlorinated fly ash, aiming at solving the defect that the prior solidification and stabilization technology treats the fly ash but does not treat the dechlorinated fly ash.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for stabilizing immobilized dechlorinated fly ash, comprising the steps of:
1) Dechlorinating the fly ash raw material by using a fly ash dechlorinating device, collecting strong alkali liquor in a cathode chamber, slurry of metal precipitates and a fly ash area, and drying the slurry of the metal precipitates and the fly ash area to obtain solid precipitates;
2) Taking rice hulls with the mass 10-15 times of that of the solid precipitates, and carrying out anoxic pyrolysis to obtain rice hull ash;
3) Mixing the rice hull ash obtained in the step 2) with the strong alkali liquor obtained in the step 1), and carrying out water bath reaction to obtain sodium silicate slurry;
4) Adding the solid precipitate obtained in the step 1) into the sodium silicate slurry obtained in the step 3), performing hydrolysis reaction, and performing centrifugal filtration to obtain a stabilized solid.
As a preferable scheme of the invention, the fly ash dechlorination device in the step 1) comprises a power supply, a fly ash area, a water washing area, a cathode chamber and an anode chamber, wherein the water washing area is arranged above the fly ash area, and the cathode chamber and the anode chamber are respectively connected with the power supply; a positive membrane is arranged between the water washing area and the cathode chamber, a negative membrane is arranged between the water washing area and the anode chamber, and the bottom of the fly ash area is in a cone shape.
As a preferable aspect of the present invention, the volume ratio of the fly ash zone to the water washing zone is 1.
As a preferable scheme of the present invention, the negative film is a slot-type plate-and-frame negative film, and the positive film is a slot-type plate-and-frame positive film.
In a preferred embodiment of the present invention, the cathode chamber is connected to the power supply via a cathode, and the cathode is a stainless steel electrode.
In a preferred embodiment of the present invention, the anode chamber is connected to the power supply via an anode, and the anode is a ruthenium-iridium-titanium electrode.
In a preferred embodiment of the present invention, the fly ash zone is provided with an agitator.
As a preferable scheme of the invention, in the step 2), the temperature of the anoxic pyrolysis is 600-700 ℃, and the time of the anoxic pyrolysis is 2-3 h.
As a preferable scheme of the invention, in the step 3), the temperature of the water bath reaction is 90-100 ℃, and the time of the water bath reaction is 1-1.5 h.
As a preferable scheme of the invention, in the step 4), the temperature of the hydrolysis reaction is 120-150 ℃, and the time of the hydrolysis reaction is 6-9 h.
In the present invention, the rice hulls contain 20% SiO 2 After anoxic pyrolysis, the rice husk epidermal cells are destroyed to reduce the internal part of the tissue and SiO 2 The degree of coupling. The rice hull ash obtained by pyrolysis has higher specific surface area, and is convenient for SiO 2 Separated therefrom.
2H (1) is mainly generated in a cathode chamber for electrolyzing and dechlorinating fly ash 2 O+2e→2OH - +H 2 ↑。
(2)M + +OH - →MOH↓。
The toxic metal ions precipitate, and the electrolysis by-products and Na + The reaction produces NaOH. The strong alkali liquor in the cathode chamber reacts with SiO2 in the rice hull in a water bath at 90-100 ℃ to generate sodium silicate. The sodium silicate reacts with Ca and A1 in the fly ash to fix the toxic heavy metal ions.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for stabilizing and fixing dechlorination fly ash, firstly, chlorine in the fly ash can be effectively removed, heavy metal is precipitated and separated out, secondary pollution caused by a water washing method is reduced, and no secondary waste is generated; secondly, a new technology for fixing dechlorinated fly ash by utilizing the waste rice hulls generated in agricultural product processing is provided, waste is treated by waste, the cost is low, and the stabilization effect is good.
Drawings
FIG. 1 is a schematic diagram of a fly ash dechlorination apparatus according to the present invention.
FIG. 2 is a process flow diagram of the present invention.
In the figure, 1, fly ash area; 2. a water washing zone; 3. a cathode chamber; 4. an anode chamber; 5. a power source; 6. a positive membrane; 7. a negative film; 8. a stirrer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Referring to fig. 1 and 2, the present invention provides a process for stabilizing immobilized dechlorinated fly ash comprising the steps of:
1) Dechlorinating the fly ash raw material by using a fly ash dechlorinating device, collecting strong alkali liquor in a cathode chamber, slurry of metal precipitates and a fly ash area, and drying the slurry of the metal precipitates and the fly ash area to obtain solid precipitates;
2) Taking rice hulls with the mass 10-15 times of that of the solid precipitates, and carrying out anoxic pyrolysis to obtain rice hull ash;
3) Mixing the rice hull ash obtained in the step 2) with the strong alkali liquor obtained in the step 1), and carrying out water bath reaction to obtain sodium silicate slurry;
4) Adding the solid precipitate obtained in the step 1) into the sodium silicate slurry obtained in the step 3), performing hydrolysis reaction, and performing centrifugal filtration to obtain a stabilized solid.
The fly ash dechlorination device comprises a power supply 5, a fly ash area 1, a water washing area 2, a cathode chamber 3 and an anode chamber 4, wherein the water washing area 2 is arranged above the fly ash area 1, the power supply 5 and the cathode chamber 3 are connected with a stainless steel electrode through a lead, and the power supply 5 and the anode chamber 4 are connected with a ruthenium iridium titanium electrode through a lead; an anode membrane 6 is arranged between the water washing area 2 and the cathode chamber 3, a cathode membrane 7 is arranged between the water washing area 2 and the anode chamber 4, the cathode chamber 3 and the anode chamber 4 are respectively positioned at two sides of the water washing area 2, the bottom of the fly ash area 1 is conical, and the water washing area 2 is cylindrical.
The volume ratio of the fly ash zone 1 to the water washing zone 2 is 1.
The negative film 7 is a slot type plate frame negative film, and the positive film 6 is a slot type plate frame positive film.
The fly ash zone 1 is also provided with an agitator 8 which passes through the water wash zone 2.
The fly ash dechlorination device adopts a secondary washing-diffusion dialysis-electrolysis method to perform dechlorination, and comprises the following steps:
1) Adding a fly ash raw material into a fly ash area, adding water with the volume 2-2.5 times that of the fly ash raw material, stirring, standing, wherein the stirring speed is 150-200 rpm, the stirring time is 15-20 min, and the standing time is 10min;
2) Respectively adding water into the anode chamber and the cathode chamber, keeping the liquid level to be level with the liquid level of the washing area, and standing;
3) Switching on the power supply, controlling the current density of the anode and the cathode, wherein the current density of the anode is 30-50A/dm 2 The current density of the cathode is 30-50A/dm 2 The time of the first electrolysis is 1.5H-2H, and H is collected 2 And Cl 2 (ii) a Adding sulfuric acid or nitric acid into the water washing area after the first electrolysis is finished, adjusting the pH to 4.5-5.0, stirring, standing, performing secondary electrolysis, and collecting H 2 And Cl 2 (ii) a Wherein, the stirring time is 15min-20min, and the standing time is 30min; the time of the second electrolysis is 1.5h-2h;
4) After dechlorination, collecting the fly ash slurry and the metal hydroxide precipitate in the cathode chamber, and drying.
Example 1
This example discloses a method for stabilizing and immobilizing dechlorinated fly ash, which selects fly ash in an incinerator of a household garbage incineration power plant, and the heavy metals in the leachate are shown in table 1.
TABLE 1 heavy metal content of the leachate
1) Weighing 600g of fly ash, dechlorinating by using a fly ash dechlorinating device through a secondary washing-diffusion dialysis-electrolysis method to obtain 414g of dechlorinated fly ash, and obtaining 11.4g of metal hydroxide precipitate and 574mL of strong alkali liquor in a cathode chamber;
2) Weighing 1kg of rice hull, and carrying out anoxic pyrolysis at 600 ℃ for 2h to obtain about 0.52kg of rice hull ash.
3) Diluting strong alkali solution in the cathode chamber to 5L (controlling pH to be more than 11), completely mixing with rice hull ash, and reacting in a water area at 90-100 ℃ for 1.5h to obtain sodium silicate slurry;
4) Adding the metal precipitate and fly ash into the sodium silicate slurry, mixing uniformly, placing in a hydrolysis kettle, heating at 150 ℃ for 8h, centrifuging, filtering, and drying to obtain 0.91kg of stabilized solid, wherein the heavy metal content in the leaching solution is shown in the following table 2.
TABLE 2 heavy metal content of the stabilized leach liquor
Example 2
This example discloses a method for stabilizing and immobilizing dechlorinated fly ash, which selects fly ash in an incinerator of a household garbage incineration power plant, and the heavy metals in the leachate are shown in Table 3.
TABLE 3 heavy metal content of the leachate
1) 632g of fly ash is weighed, a fly ash dechlorination device is utilized to carry out secondary washing-diffusion dialysis-electrolysis for dechlorination to obtain 424.4g of dechlorinated fly ash, and 12.3g of metal hydroxide precipitate and 569mL of strong alkali liquor are obtained in a cathode chamber.
2) 1kg of rice husk was weighed and pyrolysed in the absence of oxygen at 700 ℃ for 3 hours to obtain about 0.46kg of rice husk ash.
3) Diluting strong alkali solution in cathode chamber to 5L (pH is controlled to be more than 11), mixing with rice hull ash completely, and reacting in water of 90-100 deg.C for 1.5h to obtain sodium silicate slurry.
4) Adding the metal precipitate and fly ash into the sodium silicate slurry, mixing well, placing in a hydrolysis kettle, heating at 120 deg.C for 9h, centrifuging, filtering, and oven drying to obtain 0.94kg of stabilized solid, wherein the heavy metal content in the leachate is shown in Table 4 below.
TABLE 4 heavy metal content of the stabilized leach liquor
As can be seen from tables 2 and 4, the method for stabilizing and immobilizing dechlorinating fly ash of the invention firstly can effectively remove chlorine in the fly ash and simultaneously precipitate and separate out heavy metals, thereby reducing secondary pollution caused by a water washing method and having no secondary waste; secondly, a new technology for utilizing the waste rice hulls from agricultural product processing to fix dechlorinated fly ash is provided, waste is treated by waste, the cost is low, and the stabilization effect is good.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalents to the disclosed technology without departing from the spirit and scope of the present invention, and all such changes, modifications and equivalents are intended to be included therein as equivalents of the present invention; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. A method of stabilizing immobilized dechlorinated fly ash comprising the steps of:
1) Dechlorinating the fly ash raw material by using a fly ash dechlorinating device, collecting strong alkali liquor in a cathode chamber, slurry of metal precipitates and a fly ash area, and drying the slurry of the metal precipitates and the fly ash area to obtain solid precipitates;
2) Taking rice hulls with the mass 10-15 times of that of the solid precipitates, and carrying out anoxic pyrolysis to obtain rice hull ash;
3) Mixing the rice hull ash obtained in the step 2) with the strong alkali liquor obtained in the step 1), and carrying out water bath reaction to obtain sodium silicate slurry;
4) Adding the solid precipitate obtained in the step 1) into the sodium silicate slurry obtained in the step 3), performing hydrolysis reaction, and performing centrifugal filtration to obtain a stabilized solid.
2. The method of claim 1, wherein the fly ash dechlorination device in step 1) comprises a power supply, a fly ash area, a water washing area, a cathode chamber and an anode chamber, wherein the water washing area is arranged above the fly ash area, and the cathode chamber and the anode chamber are respectively connected with the power supply; a positive membrane is arranged between the water washing area and the cathode chamber, a negative membrane is arranged between the water washing area and the anode chamber, and the bottom of the fly ash area is in a cone shape.
3. A process for the stabilization of immobilized dechlorinated fly ash according to claim 2, wherein the volume ratio of the fly ash zone to the water wash zone is 1.
4. The method of claim 2, wherein the cathode film is a slotted plate and frame cathode film and the anode film is a slotted plate and frame anode film.
5. The method of claim 2, wherein the cathode chamber is connected to the power source through a cathode, and the cathode is a stainless steel electrode.
6. The method of claim 2, wherein the anode chamber is connected with the power supply through an anode, and the anode is a ruthenium-iridium-titanium electrode.
7. A process for the stabilization of immobilized dechlorinated fly ash according to claim 2, wherein the fly ash zone is provided with an agitator.
8. The method of claim 1, wherein in step 2), the temperature of anoxic pyrolysis is 600-700 ℃ and the time of anoxic pyrolysis is 2-3 h.
9. The method of claim 1, wherein the temperature of the water bath reaction in the step 3) is 90-100 ℃, and the time of the water bath reaction is 1-1.5 h.
10. The method of claim 1, wherein in the step 4), the temperature of the hydrolysis reaction is 120-150 ℃, and the time of the hydrolysis reaction is 6-9 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210638588.8A CN115228875A (en) | 2022-06-07 | 2022-06-07 | Method for stabilizing and fixing dechlorinated fly ash |
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| CN202210638588.8A CN115228875A (en) | 2022-06-07 | 2022-06-07 | Method for stabilizing and fixing dechlorinated fly ash |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117282760A (en) * | 2023-10-25 | 2023-12-26 | 北京科技大学 | Treatment method of waste incineration fly ash |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117282760A (en) * | 2023-10-25 | 2023-12-26 | 北京科技大学 | Treatment method of waste incineration fly ash |
| CN117282760B (en) * | 2023-10-25 | 2024-04-16 | 北京科技大学 | Treatment method of waste incineration fly ash |
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