CN112029999A - Acid leaching oxidation harmless treatment method for waste incineration fly ash water washing slag - Google Patents
Acid leaching oxidation harmless treatment method for waste incineration fly ash water washing slag Download PDFInfo
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- CN112029999A CN112029999A CN202010608242.4A CN202010608242A CN112029999A CN 112029999 A CN112029999 A CN 112029999A CN 202010608242 A CN202010608242 A CN 202010608242A CN 112029999 A CN112029999 A CN 112029999A
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- fly ash
- washing slag
- waste incineration
- harmless treatment
- acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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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
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for harmless treatment of washing slag of waste incineration fly ash water by acid leaching oxidation, which comprises the following steps: mixing the fly ash washing slag of waste incineration with water, wherein the liquid-solid ratio after mixing is 1: 1 to 10: pumping into a horizontal multistage stirring reactor by a pump, and then adding sulfuric acid and oxygen; evaporating and cooling the high-temperature slurry to normal temperature, and filtering to obtain filter residue as a building material raw material; and step three, the filtered filtrate contains heavy metal sulfate, so that alkaline substances such as sodium hydroxide, sodium carbonate, calcium hydroxide and the like are added. The invention has the functions of realizing heavy metal leaching and dioxin oxidative degradation in the same reactor, is convenient and simple, has no exhaust emission, and has low energy consumption; the invention adopts a horizontal multistage stirrer for reaction, is similar to a multistage stirring kettle in series connection, and has the advantages of a full-mixing kettle and a plug flow reactor.
Description
Technical Field
The invention relates to a method for treating washing slag of waste incineration fly ash water, in particular to a method for carrying out acid leaching oxidation harmless treatment on washing slag of waste incineration fly ash.
Background
With the rapid development of urban economy in China, the urban garbage yield increases day by 8-10% every year. The basic treatment modes of domestic and foreign municipal domestic garbage are landfill, incineration and composting, and the incineration method gradually becomes the trend of municipal waste treatment due to the advantages of small occupied area, short treatment time, obvious reduction (the mass reduction generally can reach 70 percent, and the volume reduction can reach 90 percent), more thorough harmless treatment, capability of recovering waste heat from garbage incineration and the like. The incineration fly ash refers to incineration residue collected in a flue gas purification system of a waste incineration plant, and accounts for about 20% of the total amount of waste incineration ash. The fly ash contains heavy metals with high leaching toxicity, soluble salts and organic chlorides (polychlorinated biphenyl and dioxin), is generally considered as a dangerous waste and has great threat to the environment. The surface and the interior of the incineration fly ash are both enriched with a large amount of heavy metals, wherein the Zn and the Pb are the most, the leaching concentration is as high as 35.84mg/L and 5.98mg/L, and the underground water quality can be seriously polluted by direct landfill.
The fly ash washing slag is solid after fly ash pretreatment, the fly ash contains sodium chloride, potassium chloride, calcium oxide, heavy metals, dioxin and other substances, the fly ash is pretreated firstly to remove soluble salts, the remaining insoluble substances such as calcium sulfate, heavy metal oxides, dioxin, iron oxide and the like are fly ash slag,
the pretreatment method specifically comprises three steps:
rinsing with water, rinsing soluble salts such as sodium chloride, potassium chloride, calcium chloride and the like in fly ash into a solution with water, and filtering to obtain washing slag, wherein the washing slag only contains a small amount of soluble salts;
and a second pretreatment method: reacting fly ash with hydrochloric acid to react calcium oxide and calcium carbonate into calcium chloride, rinsing with water to remove soluble salt in the fly ash with water, and filtering to obtain fly ash water washing residue;
and thirdly, reacting the fly ash with sulfuric acid, reacting calcium oxide and calcium carbonate in the fly ash into calcium sulfate, rinsing with water, washing soluble salt in the fly ash away with water, and filtering to obtain fly ash water washing slag.
The pretreated fly ash washing slag is mainly removed from a cement kiln for cooperative treatment or high-temperature melting at present. The cement kiln is a main method for treating fly ash water washing slag, the cement kiln can treat dioxin in fly ash by synergistic treatment, but heavy metals in the fly ash are mainly low-temperature metals such as zinc, lead and the like, the content is 0.5-1.5%, the boiling point temperature of zinc is 907 ℃, so that the heavy metals enter waste gas or are cooled by raw materials to enter cement after being completely gasified in the cement kiln (the temperature is over 1400 ℃), other heavy metals are also taken away by the waste gas in a large amount, and most of the heavy metals in the fly ash are not solidified by the cement and are transferred to the waste gas or the cement. Similar problems exist in the high-temperature melting (temperature exceeding 1200 ℃) treatment of fly ash water washing slag, and low-temperature metal in fly ash is re-gasified in a high-temperature melting state and enters waste gas, so that secondary pollution is caused. Therefore, the process route of the fly ash co-treatment of the cement kiln or the high-temperature melting treatment of the fly ash is not perfect.
Accordingly, there is a need for improvements in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a harmless treatment method for acid leaching oxidation of washing residues of waste incineration fly ash water.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for carrying out acid leaching oxidation harmless treatment on waste incineration fly ash washing slag comprises the following steps:
mixing the fly ash washing slag of waste incineration with water, wherein the liquid-solid ratio after mixing is 1: 1 to 10: pumping the mixture into a horizontal multistage stirring reactor by using a pump, then adding sulfuric acid and oxygen, wherein the mass of the sulfuric acid is 0.1-5 times of the weight of the fly ash washing slag, the mass of the oxygen is 1-10% of the mass of the fly ash washing slag, reacting at the temperature of 60-280 ℃ and under the pressure of 0.5-6 MPa for 1-10 hours, leaching and oxidizing, leaching heavy metals such as zinc, copper, nickel and cadmium on the fly ash washing slag, and oxidizing and degrading dioxin; obtaining high-temperature slurry;
evaporating and cooling the high-temperature slurry to normal temperature, and filtering to obtain filter residue as a building material raw material;
and step three, adding heavy metal sulfate in the filtered filtrate, adding alkaline substances such as sodium hydroxide, sodium carbonate, calcium hydroxide and the like, wherein the mass of the alkaline substances is 1-100% of the fly ash washing slag, adjusting the pH value to 9-11, precipitating and filtering the heavy metal carbonate or hydroxide, selling the filter slag to a zinc smelting plant, and returning the pH value of the filtrate to be neutral or further evaporating and crystallizing to obtain sulfate for sale.
The concentration of the sulfuric acid is 10-98%.
And introducing oxygen into the horizontal multistage stirring reactor until the oxygen content is as follows: 30 to 99 percent
After the sulfuric acid and the oxygen are added, the reaction temperature is 60-280 ℃ and the pressure is 0.5-6 MPa.
The alkaline matter is sodium carbonate, strong sodium oxide or calcium hydroxide.
In step one, 99% of dioxin in the slurry after the reaction was degraded.
The utility model provides a msw incineration fly ash washing slag acid leaching oxidation innocent treatment equipment, it includes sulfuric acid tank, the sulfuric acid pump, the slush pump, the water pump, the oxygenerator, horizontal multistage stirred tank, the sodium carbonate cistern, the sodium carbonate pump, sodium carbonate solution tank, the filter, fly ash sediment slush pulp tank passes through first slush pump and connects horizontal multistage stirred tank, the sulfuric acid tank passes through the sulfuric acid pump and connects horizontal multistage stirred tank, the oxygenerator connects horizontal multistage stirred tank, multistage stirred tank and mud stirred tank are connected, the mud stirred tank passes through the second slush pump and is connected with first filter, first filter is connected with the pH adjustment cauldron, sodium carbonate solution tank passes through the sodium carbonate slush pump and connects the pH adjustment cauldron, the pH adjustment cauldron passes through mother liquor pump and connects the second filter.
The working principle of the equipment for the acid leaching, oxidation and harmless treatment of the washing residue of the waste incineration fly ash water is as follows: conveying ash water washing slag slurry to a horizontal multistage stirring kettle through a slurry pump, respectively adding sulfuric acid and water into the horizontal multistage stirring kettle, outputting precipitates of the horizontal multistage stirring kettle to a stirring tank, conveying the uniformly mixed slurry to a filter through a slurry pump, removing flying ash residues after filtering to serve as building material raw materials, conveying filtrate of the filter to a pH adjusting kettle, adding a sodium carbonate solution into the pH adjusting kettle, stirring, conveying the stirred solution to the filter, filtering to obtain heavy metal precipitates, and evaporating the filtrate to obtain sodium carbonate.
The invention has the beneficial effects that:
(1) the functions of heavy metal leaching and dioxin oxidative degradation are realized in the same reactor, the reactor is convenient and simple, no waste gas is discharged, and the energy consumption is low;
(2) the reaction adopts a horizontal multistage stirrer which is similar to a multistage stirring kettle in series connection and has the advantages of a full-mixing kettle and a plug flow reactor;
(3) the whole set of process realizes continuous production, is easy to control automatically and has safe reliability.
Drawings
Fig. 1 is a schematic diagram of the present invention.
In the figure: 1. a sulfuric acid tank, 2, a sulfuric acid pump, 3, a thickener, 4, a slurry pump, 5, a water pump, 6, an oxygen generator, 7, a horizontal multistage stirring kettle, 8, a calcium hydroxide solution tank, 9, a calcium hydroxide slurry pump, 10, a solution pump, 11, a sodium carbonate solution tank, 12, a filter, 13 and a stirring tank.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and embodiments.
As shown in figure 1, the equipment for acid leaching, oxidation and harmless treatment of the washing residue of the ash incineration fly ash is characterized in that slurry obtained by treating slurry of the washing residue of the ash water through a thickener is conveyed to a horizontal multistage stirring kettle through a slurry pump, sulfuric acid and water are respectively added into the horizontal multistage stirring kettle, precipitates of the horizontal multistage stirring kettle are output to a stirring tank A, calcium hydroxide is added into the stirring tank A, the precipitates of the stirring tank A are conveyed to a filter through the slurry pump, filtrate of the filter is conveyed to a stirring tank B, a sodium carbonate solution is added into the stirring tank B and then stirred, the stirred solution is conveyed to the filter to be filtered, and the filtrate is evaporated to obtain sodium carbonate so as to obtain heavy metals.
A method for carrying out acid leaching oxidation harmless treatment on waste incineration fly ash washing slag comprises the following steps:
mixing fly ash washing slag of waste incineration with water, wherein the liquid-solid ratio of 100 g of fly ash washing slag mixed with water is 1: 1 to 10: pumping into a horizontal multistage stirring kettle by a pump, adding 75% of 100 g of sulfuric acid and 50 g of oxygen, reacting at 220 ℃ and 2MPa for 2 hours, leaching and oxidizing, leaching out heavy metals such as zinc, copper, nickel and lead on flying ash, and oxidizing and degrading dioxin;
secondly, vaporizing and cooling the high-temperature slurry, adding an alkaline substance calcium hydroxide, adjusting the pH value to be neutral, leaching out fly ash raw metal after filtering, degrading dioxin, and harmlessly treating the fly ash raw metal as a building material raw material;
and step three, adding sodium carbonate solution or sodium sulfate solution to react at first, precipitating and filtering heavy metal carbonate or sulfate, selling the solid to a zinc smelting plant, and discharging the liquid or further evaporating and crystallizing to obtain sulfate.
In the description of the present invention, it should be noted that, as the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. appear, their indicated orientations or positional relationships are based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" should be interpreted broadly, e.g., as being fixed or detachable or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art. Simple substitutions without changing the inventive content of the present invention are considered to be the same. The embodiments are described in a progressive manner in the specification, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A method for harmless treatment of waste incineration fly ash washing slag by acid leaching oxidation is characterized by comprising the following steps: the method comprises the following steps:
mixing the fly ash washing slag of waste incineration with water, wherein the liquid-solid ratio after mixing is 1: 1 to 10: pumping the mixture into a horizontal multistage stirring reactor by using a pump, then adding sulfuric acid and oxygen, wherein the mass of the sulfuric acid is 0.1-5 times of the weight of the fly ash washing slag, the mass of the oxygen is 1-10% of the mass of the fly ash washing slag, reacting at the temperature of 60-280 ℃ and under the pressure of 0.5-6 MPa for 1-10 hours, leaching and oxidizing, leaching heavy metals such as zinc, copper, nickel and cadmium on the fly ash washing slag, and oxidizing and degrading dioxin; obtaining high-temperature slurry;
secondly, the high-temperature slurry is vaporized and cooled, heavy metal of the filtered flying ash is leached, and the rest substances are used as building material raw materials;
and step three, adding an alkaline substance into the filtered solution, wherein the mass of the alkaline substance is 5-100% of that of the fly ash washing slag, adjusting the pH value to 9-11, precipitating and filtering heavy metal carbonate or hydroxide, selling the filter residue to a zinc smelting plant, and returning the pH value of the filtrate to be neutral or further evaporating and crystallizing the filtrate to obtain sulfate for sale.
2. The acid leaching oxidation harmless treatment method for the waste incineration fly ash water washing slag according to claim 1, characterized in that:
the concentration of the sulfuric acid is 10-98%.
3. The acid leaching oxidation harmless treatment method for the waste incineration fly ash water washing slag according to claim 2, characterized in that:
the content of the oxygen is as follows: 30 to 99 percent.
4. The acid leaching oxidation harmless treatment method for the waste incineration fly ash water washing slag according to claim 3, characterized in that:
after the sulfuric acid and the oxygen are added, the reaction temperature is 60-280 ℃ and the pressure is 0.5-6 MPa.
5. The acid leaching oxidation harmless treatment method for the waste incineration fly ash water washing slag according to claim 4, characterized in that:
the alkaline matter is sodium carbonate, strong sodium oxide or calcium hydroxide.
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| CN202010608242.4A CN112029999B (en) | 2020-06-29 | 2020-06-29 | Acid leaching oxidation harmless treatment method for waste incineration fly ash water washing slag |
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| CN202010608242.4A CN112029999B (en) | 2020-06-29 | 2020-06-29 | Acid leaching oxidation harmless treatment method for waste incineration fly ash water washing slag |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113215411A (en) * | 2021-04-19 | 2021-08-06 | 北京科技大学 | Harmless treatment method for waste incineration fly ash |
| CN113943011A (en) * | 2021-09-17 | 2022-01-18 | 光大环保技术研究院（深圳）有限公司 | Method for resource utilization of secondary fly ash after melting of hazardous waste plasma |
| CN113975702A (en) * | 2021-10-14 | 2022-01-28 | 昆明理工大学 | Method for removing dioxin POPs in copper smelting soot through synergistic retardation of microwave and sulfuric acid |
| WO2022203517A1 (en) * | 2021-03-24 | 2022-09-29 | Noah Solutions As | Method and apparatus for neutralizing and stabilizing of fly ash |
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| CN101708499A (en) * | 2009-12-04 | 2010-05-19 | 同济大学 | Method for jointly stabilizing fly ash and arsenic-containing waste |
| CN101863600A (en) * | 2009-04-16 | 2010-10-20 | 刘文治 | Method for removing heavy metals from activated sludge |
| CN102513329A (en) * | 2011-11-17 | 2012-06-27 | 浙江大学 | Harmless treatment method for urban garbage incineration fly ash |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1998032547A1 (en) * | 1997-01-27 | 1998-07-30 | Solvay (Societe Anonyme) | Method for refuse piling for dumping of solid residue containing heavy metals |
| CN101863600A (en) * | 2009-04-16 | 2010-10-20 | 刘文治 | Method for removing heavy metals from activated sludge |
| CN101708499A (en) * | 2009-12-04 | 2010-05-19 | 同济大学 | Method for jointly stabilizing fly ash and arsenic-containing waste |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022203517A1 (en) * | 2021-03-24 | 2022-09-29 | Noah Solutions As | Method and apparatus for neutralizing and stabilizing of fly ash |
| CN113215411A (en) * | 2021-04-19 | 2021-08-06 | 北京科技大学 | Harmless treatment method for waste incineration fly ash |
| CN113943011A (en) * | 2021-09-17 | 2022-01-18 | 光大环保技术研究院（深圳）有限公司 | Method for resource utilization of secondary fly ash after melting of hazardous waste plasma |
| CN113975702A (en) * | 2021-10-14 | 2022-01-28 | 昆明理工大学 | Method for removing dioxin POPs in copper smelting soot through synergistic retardation of microwave and sulfuric acid |
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| CN112029999B (en) | 2022-06-24 |
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