CN114147053B - Method for simultaneously removing chlorine and heavy metals from waste incineration fly ash - Google Patents

Method for simultaneously removing chlorine and heavy metals from waste incineration fly ash Download PDF

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Publication number
CN114147053B
CN114147053B CN202111182417.0A CN202111182417A CN114147053B CN 114147053 B CN114147053 B CN 114147053B CN 202111182417 A CN202111182417 A CN 202111182417A CN 114147053 B CN114147053 B CN 114147053B
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fly ash
content
waste incineration
heavy metals
incineration fly
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CN114147053A (en
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杨飞华
赵航
王肇嘉
陈梦君
郭建平
张晔
李爱红
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Southwest University of Science and Technology
Beijing Building Materials Academy of Sciences Research
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Southwest University of Science and Technology
Beijing Building Materials Academy of Sciences Research
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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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • 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 simultaneously removing chlorine and heavy metals from waste incineration fly ash, which comprises the following steps: mixing the waste incineration fly ash with an oxalic acid solution to obtain a mixture; electrolyzing the mixture under the ultrasonic condition; and after the electrolysis is finished, carrying out solid-liquid separation to obtain the treated waste incineration fly ash. The method can remove chlorine and various heavy metals in the fly ash, the Cl content in the residue can be reduced to be below 0.1 percent, the As content can be reduced to be below 2mg/Kg, the mass and the volume of the fly ash are reduced, the reduction is realized, and the treated fly ash can be further used for resource treatment.

Description

Method for simultaneously removing chlorine and heavy metals from waste incineration fly ash
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash.
Background
The waste incineration fly ash cement kiln synergistic treatment is an important direction for fly ash recycling, but the fly ash cement kiln synergistic treatment or other harmless utilization needs to carry out pretreatment on chlorine salt and heavy metal contained in the fly ash cement kiln because the waste incineration fly ash has high chlorine salt content, various heavy metals exist and extremely strong migration characteristics.
The chlorine salt in the waste incineration fly ash mainly exists in soluble chlorine salt, the water washing pretreatment is an effective method for removing the soluble chlorine salt in the fly ash, the Cl removal rate can reach about 60 percent, but the heavy metal existing in the fly ash solid phase after water washing has no obvious change, and only part of PbO and ZnO are dissolved out. Meanwhile, the washing process has obvious effect of removing soluble chlorine, but insoluble chlorine is difficult to remove by a washing method, and the process has large water demand, so that the quality of the fly ash is greatly reduced, and the improvement of the resource utilization benefit is not facilitated.
The treatment technology of heavy metals in fly ash mainly has two major directions, namely solidification and extraction. The solidification of the heavy metal refers to that the heavy metal is subjected to solidification-stabilization treatment, and compared with the original ash subjected to solidification-stabilization treatment, the volume of a finished product is usually obviously enlarged, and the storage land is increased; meanwhile, due to improper operation, a plurality of solidified blocks are easy to have serious efflorescence phenomenon during transportation and storage. Moreover, the existing curing method cannot ensure that the heavy metals are leached out again to pollute the environment when the fly ash is exposed to the environment for a long time in the future.
The extraction of the heavy metal is to separate the heavy metal from the fly ash, realize the recovery of the heavy metal and simultaneously make the fly ash become common waste or become building materials for resource utilization. The extraction method mainly comprises biological extraction, chemical extraction and the like. The heavy metal biological/chemical extraction technology has the advantages of simple process, strong operability, capability of extracting and recovering heavy metals and the like, but the cost is higher because the culture of microorganisms and the purchase of various chemical agents and chelating agents are required, the concentration of the heavy metals in the fly ash is generally very low, and the cost of the required agents cannot be offset by the recovered heavy metals.
In the previous researches, the emphasis is on the research of dechlorinating or removing heavy metals from the waste incineration fly ash, and the chlorine and the heavy metals of the fly ash can not reach the standard of a cement kiln at the same time by single technical research. Therefore, it is necessary to develop a novel harmless treatment technology for the waste incineration fly ash.
Disclosure of Invention
The invention provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, which can solve the problem of removing chlorine and heavy metals from fly ash step by step in the past, is convenient and quick and saves time.
Specifically, the invention provides the following technical scheme:
a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash comprises the following steps:
mixing the waste incineration fly ash with an oxalic acid solution to obtain a mixture;
electrolyzing the mixture under the ultrasonic condition;
and after the electrolysis is finished, carrying out solid-liquid separation to obtain the treated waste incineration fly ash.
The invention discovers that the removal efficiency of chlorine and heavy metals in the fly ash can be obviously improved by introducing the waste incineration fly ash into oxalic acid solution with proper concentration and electrolyzing under the ultrasonic condition.
Preferably, in the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash provided by the invention, the current density is controlled to be 50-250 mA/cm during electrolysis 2 Electrolysis is preferably carried out at a constant current density.
Preferably, in the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, the electrode exchange frequency of electrolysis is 30-50Hz. The electrode exchange frequency is also called electrode polarity exchange frequency, electrode exchange frequency or polarity exchange frequency, and refers to the number of times that the current direction changes when the positive electrode and the negative electrode are exchanged in unit time when a power supply is output, and f =1/T.
Preferably, in the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash provided by the invention, the molar concentration of the oxalic acid solution is 0.1-2 mol/L.
Preferably, in the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash provided by the invention, the mass ratio of the waste incineration fly ash to the oxalic acid solution is 1: (5-20).
Preferably, in the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash provided by the invention, the ultrasonic frequency of the ultrasonic wave is 10-30 KHz.
Preferably, in the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash provided by the invention, the mixed material is electrolyzed under the conditions of ultrasound and stirring, and further preferably, the stirring speed is 100-300 r/min.
Preferably, in the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash provided by the invention, the particle size of the waste incineration fly ash is less than 100 μm.
Preferably, the method for simultaneously removing chlorine and heavy metals from waste incineration fly ash provided by the invention further comprises the following steps before mixing: and drying the waste incineration fly ash.
The invention has the following beneficial effects:
according to the method provided by the invention, chlorine and various heavy metals in the fly ash can be removed, the Cl content in the residue can be reduced to be below 0.1%, the As content can be reduced to be below 2mg/Kg, the mass and the volume of the fly ash are reduced, the reduction is realized, and the treated fly ash can be further used for resource treatment;
according to the method provided by the invention, heavy metal ions are reduced at the cathode, anions are oxidized at the anode, the treatment efficiency is high, and valuable chemicals or metals are recycled;
according to the method provided by the invention, free radicals generated by the reaction can directly react with organic pollutants and can be degraded into CO 2 、H 2 O and simple low molecular organics, with no or little secondary pollution.
Drawings
FIG. 1 is a schematic flow diagram of the process for removing chlorine and heavy metals provided in example 1.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples, the equipment and the like used are conventional products which are available from normal commercial vendors, not indicated by manufacturers. The process is conventional unless otherwise specified, and the starting materials used are commercially available from published sources.
An electrolytic reaction device: the electrolytic reaction is carried out in a 300mL beaker, a KR300W series single-path output power supply of Shenzhen Jinzhou electronic technology Limited company is adopted, positive and negative polar plates are graphite plates with the size of 4.5 multiplied by 10cm, and the distance between the polar plates is 20 mm. An ultrasonic probe of the ultrasonic generator extends into the beaker, and a magnetic rotor is arranged in the beaker.
In the following examples, the fly ash material used was from a municipal solid waste incineration plant, and the Cl content was 16.55%, the As content was 11.15mg/Kg, the Cr content was 82.13mg/Kg, the Ni content was 21.06mg/Kg, the Mn content was 411.13mg/Kg, and the Zn content was 3317.78mg/Kg.
The method for testing the chloride ion content and the heavy metal content comprises the following steps:
content of chloride ion: the content of chloride ion was measured according to JIS A1154. Mixing 65% nitric acid and distilled water according to a volume ratio of 1:6 to prepare a nitric acid (1+6) reagent; adding 70mL of nitric acid (1+6) reagent into 10g of a sample to be detected, magnetically stirring for 30min, heating to boil for about 5min, and cooling to normal temperature; filtering with a vacuum filtration device, and taking filtrate to constant volume; and (4) measuring the content of chloride ions in the filtrate after constant volume by adopting an ICS1000 ion chromatograph.
Heavy metal content: weighing a sample to be detected, carrying out digestion reaction, adding a certain amount of nitric acid, hydrochloric acid and hydrofluoric acid, carrying out digestion in a digestion instrument, removing acid to 1-2mL after the digestion is finished, and then carrying out constant volume to 50mL. Wherein the addition amount of nitric acid is 1g/60L, the addition amount of hydrochloric acid is 1g/20L, the addition amount of hydrofluoric acid is 1g/20L, and the temperature for removing the acid is 120-150 ℃. The volume is determined by 1% nitric acid solution. And filtering the liquid after constant volume, and determining the concentration of heavy metal in the digestion solution by adopting an ICP-OES type inductively coupled plasma full-automatic atomic emission spectrometer.
Example 1
Example 1 provides a process for the simultaneous removal of chlorine and heavy metals from fly ash from waste incineration, the steps of which are as follows (partly with reference to figure 1):
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight and accurately recording the weight, wherein the weight is 19.0213g.
And (4) measuring the contents of chlorine and heavy metals in the filter residue. It was found that the content of Cl in the residue was 0.08%, the content of As was 1.10mg/Kg, the content of Cr was 69.95mg/Kg, the content of Ni was 14.59mg/Kg, the content of Mn was 246.65mg/Kg, and the content of Zn was 2331.88mg/Kg.
Example 2
Example 2 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 4.84V, the electrode exchange frequency is 40Hz, and the current density is 100mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 19.7561g.
And (4) measuring the contents of chlorine and heavy metals in the filter residue. It was found that the Cl content in the residue was 0.073%, the As content was 1.29mg/Kg, the Cr content was 68.95mg/Kg, the Ni content was 15.70mg/Kg, the Mn content was 218.81mg/Kg, and the Zn content was 2377.29mg/Kg.
Example 3
Example 3 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 6.58V, the electrode exchange frequency is 40Hz, and the current density is 150mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 19.9930g.
And (4) measuring the contents of chlorine and heavy metals in the filter residue. It was found that the Cl content of the residue was 0.039%, the As content was 2.09mg/Kg, the Cr content was 65.99mg/Kg, the Ni content was 15.39mg/Kg, the Mn content was 219.33mg/Kg, and the Zn content was 1740.17mg/Kg.
Example 4
Example 4 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) The fly ash from a domestic waste incineration plant is subjected to ball milling, uniform mixing and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 7.53V, the electrode exchange frequency is 40Hz, and the current density is 200mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 19.4678g.
And (4) measuring the contents of chlorine and heavy metals in the filter residue. It was found that the content of Cl in the residue was 0.038%, the content of As was 0.48mg/Kg, the content of Cr was 60.47mg/Kg, the content of Ni was 10.75mg/Kg, the content of Mn was 202.68mg/Kg, and the content of Zn was 1327.47mg/Kg.
Example 5
Example 5 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 9.20V, the electrode exchange frequency is 40Hz, and the current density is 250mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 19.9610g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the content of Cl in the residue was 0.026%, the content of As was 1.97mg/Kg, the content of Cr was 61.92mg/Kg, the content of Ni was 11.33mg/Kg, the content of Mn was 209.14mg/Kg, and the content of Zn was 1232.16mg/Kg.
Example 6
Example 6 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) The fly ash from a domestic waste incineration plant is subjected to ball milling, uniform mixing and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.05mol/L according to the liquid-solid ratio of 10 to obtain a mixture;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 13.5610g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.19%, the As content was 14.34mg/Kg, the Cr content was 105.70mg/Kg, the Ni content was 28.54mg/Kg, the Mn content was 521.15mg/Kg, and the Zn content was 4053.11mg/Kg.
Example 7
Example 7 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.25mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 12.0513g.
And (4) measuring the contents of chlorine and heavy metals in the filter residue. It was found that the Cl content in the residue was 0.13%, the As content was 12.51mg/Kg, the Cr content was 121.67mg/Kg, the Ni content was 22.80mg/Kg, the Mn content was 349.31mg/Kg, and the Zn content was 3604.81mg/Kg.
Example 8
Example 8 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.75mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 19.0114g.
And (4) measuring the contents of chlorine and heavy metals in the filter residue. It was found that the Cl content in the residue was 0.05%, the As content was 1.41mg/Kg, the Cr content was 58.34mg/Kg, the Ni content was 11.10mg/Kg, the Mn content was 150.95mg/Kg, and the Zn content was 1521.78mg/Kg.
Example 9
Example 9 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 1mol/L according to the liquid-solid ratio of 10 to obtain a mixture;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 1 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 19.4149g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the content of Cl in the residue was 0.15%, the content of As was 1.12mg/Kg, the content of Cr was 47.24mg/Kg, the content of Ni was 9.85mg/Kg, the content of Mn was 162.99mg/Kg, and the content of Zn was 1233.04mg/Kg.
Example 10
Example 10 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) The fly ash from a domestic waste incineration plant is subjected to ball milling, uniform mixing and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 0.5 hour, filtering, drying the filter residue to constant weight, and accurately recording the weight of 19.6998g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.92%, the As content was 2.26mg/Kg, the Cr content was 60.34mg/Kg, the Ni content was 11.15mg/Kg, the Mn content was 240.04mg/Kg, and the Zn content was 2089.48mg/Kg.
Example 11
Example 11 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the steps of:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After reacting for 2 hours, filtering, drying the filter residue to constant weight and accurately recording the weight of 19.0213g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.88%, the As content was 1.62mg/Kg, the Cr content was 68.43mg/Kg, the Ni content was 9.74mg/Kg, the Mn content was 160.97mg/Kg, and the Zn content was 2314.87mg/Kg.
Example 12
Example 12 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After 4 hours of reaction, the mixture was filtered, and the residue was dried to a constant weight and the weight was accurately recorded as 18.9876g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.84%, as content was 0.47mg/Kg, cr content was 61.97mg/Kg, ni content was 7.92mg/Kg, mn content was 148.63mg/Kg, and Zn content was 1492.42mg/Kg.
Example 13
Example 13 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the steps of:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 40Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic is 20KHz; the stirring speed is 150r/min;
(3) After 8 hours of reaction, filtering is carried out, the filter residue is dried to constant weight, and the weight is accurately recorded, namely 17.9051g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.56%, the As content was 1.79mg/Kg, the Cr content was 63.27mg/Kg, the Ni content was 6.93mg/Kg, the Mn content was 153.81mg/Kg, and the Zn content was 1601.45mg/Kg.
Example 14
Example 14 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 0Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz;the stirring speed is 150r/min;
(3) After 4 hours of reaction, filtering is carried out, the filter residue is dried to constant weight, and the weight is accurately recorded, namely 19.1535g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.14%, the As content was 8.46mg/Kg, the Cr content was 64.79mg/Kg, the Ni content was 12.27mg/Kg, the Mn content was 232.62mg/Kg, and the Zn content was 2036.41mg/Kg.
Example 15
Example 15 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 20Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After 4 hours of reaction, the mixture was filtered, and the residue was dried to a constant weight and the weight was accurately recorded as 19.0134g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.04%, the As content was 7.44mg/Kg, the Cr content was 66.60mg/Kg, the Ni content was 12.83mg/Kg, the Mn content was 219.20mg/Kg, and the Zn content was 2108.21mg/Kg.
Example 16
Example 16 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: voltage of about 2.0V, electrodeThe exchange frequency was 60Hz, and the current density was 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After 4 hours of reaction, the mixture was filtered, and the residue was dried to a constant weight and the weight was accurately recorded as 19.6045g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the Cl content in the residue was 0.03%, the As content was 2.04mg/Kg, the Cr content was 57.35mg/Kg, the Ni content was 12.37mg/Kg, the Mn content was 153.61mg/Kg, and the Zn content was 1516.06mg/Kg.
Example 17
Example 17 provides a method for simultaneously removing chlorine and heavy metals from waste incineration fly ash, comprising the following steps:
(1) And performing ball milling and uniform mixing on the fly ash from the household garbage incineration plant, and drying. Taking 20g of a sample, and adding an oxalic acid solution with the concentration of 0.5mol/L according to the liquid-solid ratio of 10;
(2) Electrolyzing the mixture under the conditions of ultrasound and stirring; the conditions of the electrolysis are as follows: the voltage is about 2.0V, the electrode exchange frequency is 80Hz, and the current density is 50mA/cm 2 (ii) a The ultrasonic frequency of the ultrasonic wave is 20KHz; the stirring speed is 150r/min;
(3) After 4 hours of reaction, the mixture was filtered, and the residue was dried to a constant weight and the weight was accurately recorded as 19.1310g.
And (4) measuring the contents of chlorine and heavy metal in the filter residue. It was found that the residue had a Cl content of 0.03%, an As content of 2.29mg/Kg, a Cr content of 56.82mg/Kg, a Ni content of 12.78mg/Kg, an Mn content of 166.01mg/Kg, and a Zn content of 1325.67mg/Kg.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.

Claims (8)

1. A method for simultaneously removing chlorine and heavy metals from waste incineration fly ash is characterized by comprising the following steps:
mixing the waste incineration fly ash with an oxalic acid solution to obtain a mixture;
electrolyzing the mixture under the ultrasonic condition;
after the electrolysis is finished, carrying out solid-liquid separation to obtain treated waste incineration fly ash;
the electrode exchange frequency of the electrolysis is 30-50Hz;
the molar concentration of the oxalic acid solution is 0.5 to 1mol/L.
2. The method for simultaneously removing chlorine and heavy metals from waste incineration fly ash according to claim 1, wherein the current density of electrolysis is 50 to 250mA/cm 2 。
3. The method for simultaneously removing chlorine and heavy metals from waste incineration fly ash according to claim 1 or 2, wherein the mass ratio of the waste incineration fly ash to the oxalic acid solution is 1: (5 to 20).
4. The method for simultaneously removing chlorine and heavy metals from waste incineration fly ash according to claim 1 or 2, wherein the ultrasonic frequency of the ultrasonic is 10 to 30KHz.
5. The method for simultaneously removing chlorine and heavy metals from waste incineration fly ash according to claim 1 or 2, characterized in that the mixture is subjected to the electrolysis under ultrasonic, stirring conditions.
6. The method for simultaneously removing chlorine and heavy metals from waste incineration fly ash according to claim 5, wherein the stirring speed is 100 to 300r/min.
7. The method for simultaneously removing chlorine and heavy metals from waste incineration fly ash according to claim 1 or 2, wherein the particle size of the waste incineration fly ash is 100 μm or less.
8. The method for simultaneously removing chlorine and heavy metals from fly ash from waste incineration as claimed in claim 1 or 2, further comprising, before mixing:
and drying the waste incineration fly ash.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006158987A (en) * 2004-12-02 2006-06-22 Miyoshi Oil & Fat Co Ltd Method for removing heavy metal in marine product processing residue
JP2008264627A (en) * 2007-04-17 2008-11-06 Pollars Laboratory Corp Waste treatment material and treatment method for detoxifying fly ash (soot and dust) and burned ash or the like
JP2014163843A (en) * 2013-02-26 2014-09-08 Toshiba Corp Cleaning acid recycling method and recycling facility
CN104785505A (en) * 2015-04-29 2015-07-22 重庆大学 Method for removing heavy metals in municipal solid waste incineration fly ash
CN112473657A (en) * 2020-12-07 2021-03-12 北京建筑材料科学研究总院有限公司 Low-vanadium catalyst for synergistically removing dioxin and mercury in flue gas and preparation method and application thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2501284C3 (en) * 1975-01-15 1980-06-12 Duisburger Kupferhuette, 4100 Duisburg Process for the processing of manganese nodules and recovery of the valuable substances they contain
JP3962855B2 (en) * 2001-07-19 2007-08-22 日立造船株式会社 Recovery method of heavy metals from fly ash
CN204298476U (en) * 2014-06-17 2015-04-29 中山大学 A kind of modified electrode ultrasonic assistant in-pulp electrolysis device
CN105297078A (en) * 2014-06-17 2016-02-03 中山大学 Ultrasonic-assisted pulp electrolysis method for tailing sand
CN207138475U (en) * 2017-05-19 2018-03-27 天津壹新环保工程有限公司 A kind of low energy consumption making fly-ash from incineration harmless processing unit
CN111268771A (en) * 2020-02-17 2020-06-12 北京科技大学 Electrochemical method for dechlorinating and removing heavy metals from incineration fly ash water washing liquid
CN112266188A (en) * 2020-10-27 2021-01-26 浙江中陶环保科技集团有限公司 Method for preparing phosphorus modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash
CN112792099B (en) * 2020-12-29 2022-10-11 江苏智诚达环保科技有限公司 Method for removing pollutants in fly ash and recycling pollutants

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006158987A (en) * 2004-12-02 2006-06-22 Miyoshi Oil & Fat Co Ltd Method for removing heavy metal in marine product processing residue
JP2008264627A (en) * 2007-04-17 2008-11-06 Pollars Laboratory Corp Waste treatment material and treatment method for detoxifying fly ash (soot and dust) and burned ash or the like
JP2014163843A (en) * 2013-02-26 2014-09-08 Toshiba Corp Cleaning acid recycling method and recycling facility
CN104785505A (en) * 2015-04-29 2015-07-22 重庆大学 Method for removing heavy metals in municipal solid waste incineration fly ash
CN112473657A (en) * 2020-12-07 2021-03-12 北京建筑材料科学研究总院有限公司 Low-vanadium catalyst for synergistically removing dioxin and mercury in flue gas and preparation method and application thereof

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