CN112090923A - Harmless co-processing method for applying microwave hydrothermal method to fly ash and electroplating wastewater - Google Patents
Harmless co-processing method for applying microwave hydrothermal method to fly ash and electroplating wastewater Download PDFInfo
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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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
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/30—Incineration ashes
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a harmless co-disposal method for applying a microwave hydrothermal method to fly ash and electroplating wastewater. And adding the fly ash after washing, a certain amount of additive and wastewater into a sealed polytetrafluoroethylene container, performing microwave heating to stabilize and degrade heavy metals and dioxin in the fly ash and the wastewater, and simultaneously, directly burying the treated product as household garbage or as an adsorbent to realize primary resource utilization. After the treatment by the method, the leaching concentration of the heavy metals in the fly ash is far lower than the limit value of GB16889-2008, the degradation rate of dioxin is higher than 93%, the removal rate of the heavy metals in the wastewater is higher than 99%, and the co-treatment product still has strong adsorbability. The invention can realize harmless treatment and resource utilization of dangerous wastes such as fly ash, wastewater and the like at the same time, has high efficiency, low energy consumption and strong practicability, and has extremely high practical application potential of large-scale treatment.
Description
Technical Field
The invention relates to the fields of microwave heating application and hazardous waste disposal and recycling application, in particular to a harmless co-disposal method for applying a microwave hydrothermal method to fly ash and electroplating wastewater.
Background
With the increasing popularity of waste incineration disposal, the fly ash output of waste incineration in China also increases. Since the fly ash contains a large amount of heavy metals, chlorinated organic compounds, sulfides, dioxins and other toxic and harmful components, the hazardous waste which is specified as the serial number HW18 by the national hazardous waste records must be properly disposed. Conservative estimation shows that the fly ash amount generated by urban domestic garbage incineration in China is more than 600 million tons by the end of 2020, and the contradiction between the rapid increase of the fly ash yield of garbage incineration and the realization of efficient harmless treatment is increasingly prominent. Meanwhile, the electroplating wastewater in China has huge yield and complex components, and a large amount of heavy metal and organic pollutants contained in the electroplating wastewater greatly improve the treatment difficulty and the process requirement.
Compared with developed countries, fly ash disposal technology in China is relatively laggard, mainly by cement solidification and chemical agent stabilization. The cement solidification technology is the most traditional fly ash treatment method, simple process equipment and operation, and low disposal cost, and is the greatest advantage, and cement solidification still occupies a great proportion in undeveloped countries. For the stabilization of the medicament, due to the complexity of the components of the fly ash from the incineration of the municipal solid waste and the form of heavy metals, a generally applicable chemical stabilizer is difficult to find, the stabilization effect of the solidification of the medicament on dioxin is small, the dehydration filtrate after the treatment of the fly ash contains soluble salts and suspended heavy metals, secondary treatment is needed, otherwise secondary pollution is possibly caused, and the main reason is that the large-scale application of the stabilization of the medicament is restricted. Although the heat treatment technology has unique advantages in the aspects of heavy metal fixation and dioxin removal rate, the high equipment, high capital and high cost investment are key factors for restricting the global application of the heat treatment technology, so that the heat treatment technology is widely applied to developed regions at present.
Aiming at the defects of the existing disposal technology, the invention provides a harmless co-disposal method for applying a hydrothermal method of microwave-assisted heating to fly ash and electroplating wastewater based on the treatment requirement of the electroplating wastewater by taking the reinforced disposal effect, the reduced disposal cost and the simplified disposal process as guide ideas, and obtains a product with economic utilization value.
Disclosure of Invention
The invention aims to provide a harmless co-disposal method of waste incineration fly ash and electroplating wastewater, which has better disposal effect and lower disposal cost, provides technical support for large-scale disposal of dangerous wastes such as household waste incineration fly ash, electroplating wastewater and the like, and realizes resource recycling of wastes while relieving increasingly severe harmless disposal pressure of fly ash and wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a harmless co-processing method for applying a microwave hydrothermal method to fly ash and electroplating wastewater comprises the following steps: the fly ash after the water washing pretreatment is mixed with a certain amount of additives and electroplating wastewater to obtain mortar, the mortar is added into a sealed polytetrafluoroethylene container and is subjected to microwave heating, so that organic pollutants such as heavy metals and dioxin in the fly ash and the wastewater are stabilized and degraded, meanwhile, the product obtained after the treatment is subjected to solid-liquid separation, the waste liquid can be directly used as household garbage for landfill, and the waste solid can be used as an adsorbent for recycling after being dried, so that the waste is recycled.
Preferably, before the electroplating wastewater is mixed with the fly ash, the content of cyanide in the electroplating wastewater needs to be detected, if the content of cyanide in the electroplating wastewater is higher than 0.5mg/L, hydrogen peroxide is added into the electroplating wastewater containing cyanide for oxidation treatment, and otherwise, the electroplating wastewater does not need to be treated.
Preferably, the fly ash is subjected to water washing pretreatment before being added into the closed container, so that inorganic chlorine elements in the fly ash are removed.
Preferably, electroplating wastewater is adopted to replace a conventional aqueous solution, hydrothermal conditions are provided for microwave reaction, the electroplating wastewater contains heavy metal ions, and the heavy metal ions are one or more of Pb ions, Cu ions, Cr ions, Cd ions, Ni ions and Zn ions.
Preferably, the additive is soluble phosphate, the dosage of the soluble phosphate required to be added per kilogram of fly ash is 0.05-0.1mol, and the dosage of the electroplating wastewater required to be added per kilogram of fly ash is 1-2L. The soluble phosphate is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
Preferably, the microwave heating temperature is 200 ℃ to 250 ℃, more preferably 210 ℃ to 230 ℃, and still more preferably 220 ℃.
Preferably, the microwave heating time is 1-2h, more preferably 60-90min, and still more preferably 90 min.
Compared with the prior art, the invention has the following advantages:
(1) on one hand, the soluble phosphate with low price is used as the additive, and the mixed additive not only can realize the stabilization of heavy metals in the fly ash and the adsorption of the heavy metals in the wastewater, but also can promote the degradation of dioxin by influencing the activity of heavy metal ions, thereby improving the degradation rate of the fly ash and the dioxin in the wastewater. Meanwhile, the harmless treatment of substances such as heavy metal, dioxin and the like in waste incineration fly ash and wastewater is realized, and a major breakthrough of recycling hazardous waste treatment products as adsorbents is realized.
On the basis of the mixed additive, the invention combines the water washing pretreatment and microwave hydrothermal treatment technology, under the microwave action, dioxin in the fly ash has violent chlorination synthesis reaction, and octa-chloro furan in the product is multiplied. Because the inorganic chlorine atoms in the fly ash can participate in the synthesis and decomposition reaction of dioxin molecules, the microwave degradation of the dioxin is not very facilitated. Therefore, the invention provides a pretreatment method by using water washing, aims to remove inorganic chlorine elements in the fly ash, generates a blocking effect on the chlorination reaction of dioxin, and further greatly improves the degradation efficiency of the dioxin.
Although water washing is a conventional pretreatment means, no report that water washing pretreatment is applied to microwave degradation of dioxin exists so far, and the treatment mode of the invention achieves breakthrough technical effects.
The stabilizing mechanism of microwave hydrothermal to heavy metals can be expressed as:
SiO2→H2SiO4 2- (1)
Al2O3→Al(OH)4 - (2)
Ca(OH)2→Ca(OH)+ (3)
Ca(OH)++Ca2++PO4 3-→Ca10(PO4)6(OH)2 (4)
Ca(OH)++Al(OH)4 -+H2SiO4 2-→CaAl2Si2O8 (5)
under the action of microwaves, the mixed mortar can quickly synthesize zeolite-like substances, and the synthesized zeolite-like substances can wrap and adsorb heavy metals in fly ash and wastewater, so that the adsorption and stabilization effects of the heavy metals in the fly ash and the wastewater are improved. Although there is consensus on the increase of the adsorbability of the product after hydrothermal treatment, the invention introduces the microwave-assisted heating technology into the hydrothermal method, the obtained waste incineration fly ash treatment product has extremely strong adsorbability (the adsorbability of the treatment product is improved by 30 times), the waste incineration fly ash treatment product is far superior to the conventional fly ash hydrothermal treatment product, the resource utilization can be realized, the cation exchange amount of the waste incineration fly ash treatment product is as high as 0.804meq/g, and even exceeds part of artificial zeolite, such as cancrinite, nepheline, kalsilite and the like.
In conclusion, the preparation process of the adsorbent is integrated with the conventional process of adsorbing heavy metals in wastewater, so that in-situ removal is realized. The invention realizes harmless treatment and resource utilization of solid hazardous waste and liquid waste water simultaneously, is a major breakthrough, greatly simplifies the treatment process, and provides a tamping theory and practice basis for the industrial development of dangerous waste treatment of fly ash, waste water and the like.
(2) On the other hand, the additive dosage required by the invention for each kilogram of waste incineration fly ash is only 0.05-0.1mol, the temperature required by microwave heating is 200-250 ℃, and the duration is 1-2h, compared with other dioxin treatment methods, the method greatly reduces the reaction temperature and the reaction time, and is a great advantage of the invention.
After the treatment by the process, the removal efficiency of various heavy metals in the wastewater reaches up to 99%, the dioxin degradation rate can also reach more than 93%, the toxicity of the dioxin degradation rate is far lower than the requirement of the domestic garbage landfill standard (GB16889-2008), and the treated product has extremely strong environmental stability and safety. The adsorbent property of the treated product can realize zero emission of solid waste and create new economic value, thereby further reducing the treatment cost and enabling the creation value of the invention to be more suitable for the national conditions of China.
The advantages of the present invention will be further apparent in the following practical examples.
Drawings
FIG. 1 is a flow chart of the handling method of the present invention.
Detailed Description
Example 1
Raw materials: the waste incineration fly ash to be treated has the following primary leaching concentration of main heavy metals: cd 0.6025mg/L, Cu 4.159mg/L, Ni 0.2819mg/, Pb 0.4639mg/L and Zn 52.40 mg/L; the concentration of dioxin contained is as follows: 180.9ng/g, and the toxicity equivalent is 2.601 ng/g; the concentration of main pollutants contained in electroplating wastewater of a certain project is as follows: cr: 80mg/L, Ni: 70mg/L, Cu: 30mg/L, total cyanide: 30mg/L and a pH of about 2 to 6.
Pretreatment: the wastewater is pretreated by an oxidation method (hydrogen peroxide) to remove cyanide.
The treatment method comprises the following steps: the main flow is detailed in FIG. 1. The garbage to be treated is incinerated, fly ash is washed for standby, and then 1kg of fly ash and 0.05mol of Na are added2HPO4And 2L of electroplating wastewater are respectively added into a closed container and uniformly mixed, and the mixture is treated by microwave at 220 ℃ for 60And (3) performing liquid-solid separation after minutes, and drying to obtain a harmless product (adsorbent).
The analysis process comprises the following steps: measuring the leaching concentration of heavy metals in the dried solid product by adopting a solid waste leaching toxicity leaching method, namely an acetic acid buffer solution method (HJ/T300-2007); determining the concentration of heavy metal in the wastewater after the co-treatment; analyzing the content of dioxin by adopting a high-resolution gas chromatography/high-resolution mass spectrometer (HRGC/MS); detecting the content of cyanide by adopting a spectrophotometry method; and (3) carrying out cation exchange amount detection and heavy metal adsorption experimental study on the solid product.
And (3) measuring results: heavy metal leaching results of solid product: cd 0.0451mg/L, Cu 1.2204mg/L, Ni 0.1247mg/L, Pb 0.0728mg/L, Zn 2.411mg/L, toxicity equivalent of dioxin: 0.198 ng/g; cation exchange amount: 0.766 meq/g; the concentrations of all substances after the co-treatment of the electroplating wastewater are as follows: cr: 0.2567mg/L, Ni: 0.1351mg/L, Cu: 0.2514mg/L, total cyanide: 0.1053mg/L (the emission standard required by the engineering is that Cr is 1.0mg/L, Ni: 0.5mg/L, Cu: 0.5mg/L and total cyanide is 0.3 mg/L).
And (4) conclusion: under the condition, the heavy metal stabilization degree is extremely high; the degradation rate of the dioxin exceeds 92 percent, so that the toxicity of the dioxin is far lower than the requirement of the domestic garbage landfill standard; the adsorbability of the treated product is improved by more than 30 times, and the treatment effect of the electroplating wastewater completely meets the actual engineering requirements. Therefore, the toxicity of the treated product is greatly reduced in the aspects of heavy metal content and dioxin concentration, the in-situ removal of pollutants contained in the actual electroplating wastewater can be completed simultaneously, and the product still has the application prospect of recycling in the form of an adsorbent.
(the wastewater of this example was obtained by experimental preparation based on actual wastewater of engineering modification of environmental protection design institute of Fujian province, Ltd. in published literature)
Example 2
Raw materials: the waste incineration fly ash to be treated has the following primary leaching concentration of main heavy metals: cd 0.6025mg/L, Cu 4.159mg/L, Ni 0.2819mg/, Pb 0.4639mg/L and Zn 52.40 mg/L; the concentration of dioxin contained is as follows: 180.9ng/g, and the toxicity equivalent is 2.601 ng/g; the main pollutant concentrations contained in the relevant water quality projects of a certain company are as follows: cr: 60mg/L, Ni: 30mg/L, Cu: 40mg/L, Pb: 1mg/L, Zn: 80mg/L, total cyanide: 20mg/L and a pH of about 6 to 9.
Pretreatment: the wastewater is pretreated by an oxidation method (hydrogen peroxide) to remove cyanide.
The treatment method comprises the following steps: the main flow is detailed in FIG. 1. The garbage to be treated is incinerated, fly ash is washed for standby, and then 1kg of fly ash and 0.05mol of Na are added2HPO4And 2L of electroplating wastewater are respectively added into a closed container to be uniformly mixed, the mixture is treated by microwave for 80 minutes at the temperature of 220 ℃, then liquid-solid separation is carried out, and a harmless product (adsorbent) can be obtained after drying.
The analysis process comprises the following steps: measuring the leaching concentration of heavy metals in the dried solid product by adopting a solid waste leaching toxicity leaching method, namely an acetic acid buffer solution method (HJ/T300-2007); determining the concentration of heavy metal in the wastewater after the co-treatment; analyzing the content of dioxin by adopting a high-resolution gas chromatography/high-resolution mass spectrometer (HRGC/MS); detecting the content of cyanide by adopting a spectrophotometry method; and (3) carrying out cation exchange amount detection and heavy metal adsorption experimental study on the solid product.
And (3) measuring results: heavy metal leaching results of solid product: cd 0.0512mg/L, Cu 1.024mg/L, Ni 0.1507mg/L, Pb 0.0539mg/L, Zn 2.268mg/L, dioxin toxicity equivalent: 0.173 ng/g; cation exchange amount: 0.795 meq/g; the concentration of each substance after the co-treatment of the wastewater is as follows: cr: 0.2374mg/L, Ni: 0.1125mg/L, Cu: 0.2547mg/L, Pb: 0.0011mg/L, Zn: 0.2342mg/L, total cyanide: 0.0867 mg/L.
And (4) conclusion: under the condition, the heavy metal stabilization degree is extremely high; the degradation rate of the dioxin exceeds 93 percent, so that the toxicity of the dioxin is far lower than the requirement of the domestic garbage landfill standard; the adsorbability of the treated product is improved by more than 30 times, and the treatment effect of the electroplating wastewater completely meets the actual engineering requirements.
(the wastewater of this example was obtained from a network data, a water quality project related to Suzhou precious metals recovery Co., Ltd., and obtained by carrying out an experimental arrangement)
Example 3
Raw materials: the waste incineration fly ash to be treated has the following primary leaching concentration of main heavy metals: cd 0.6025mg/L, Cu 4.159mg/L, Ni 0.2819mg/, Pb 0.4639mg/L and Zn 52.40 mg/L; the concentration of dioxin contained is as follows: 180.9ng/g, and the toxicity equivalent is 2.601 ng/g; the concentration of main pollutants in the wastewater of a certain surface treatment plant is as follows: cr: 166mg/L, pH about 5.
The treatment method comprises the following steps: the main flow is detailed in FIG. 1. The garbage to be treated is incinerated, fly ash is washed for standby, and then 1kg of fly ash and 0.05mol of Na are added2HPO4And 2L of electroplating wastewater are respectively added into a closed container to be uniformly mixed, the mixture is treated by microwave for 60 minutes at the temperature of 230 ℃, then liquid-solid separation is carried out, and a harmless product (adsorbent) can be obtained after drying.
The analysis process comprises the following steps: measuring the leaching concentration of heavy metals in the dried solid product by adopting a solid waste leaching toxicity leaching method, namely an acetic acid buffer solution method (HJ/T300-2007); determining the concentration of heavy metal in the wastewater after the co-treatment; analyzing the content of dioxin by adopting a high-resolution gas chromatography/high-resolution mass spectrometer (HRGC/MS); and (3) carrying out cation exchange amount detection and heavy metal adsorption experimental study on the solid product.
And (3) measuring results: heavy metal leaching results of solid product: cd 0.0634mg/L, Cu 1.135mg/L, Ni 0.1438mg/L, Pb 0.0452mg/L, Zn 2.137mg/L, dioxin toxicity equivalent: 0.169 ng/g; cation exchange amount: 0.788 meq/g; concentration of pollutants after co-treatment of wastewater: cr: 0.4486 mg/L.
And (4) conclusion: under the condition, the heavy metal stabilization degree is extremely high; the degradation rate of the dioxin exceeds 93 percent, so that the toxicity of the dioxin is far lower than the requirement of the domestic garbage landfill standard; the adsorbability of the treated product is improved by more than 30 times; the effect of removing Cr ions in the electroplating wastewater is higher than 99 percent, and the practical engineering requirements are completely met.
(the wastewater of this example was obtained from a publicly-published work, washing water of a chromium electroplating plant of a surface treatment plant of Changsha, and passivating wastewater of that company, which were experimentally disposed)
Example 4
Raw materials: the waste incineration fly ash to be treated has the following primary leaching concentration of main heavy metals: cd 0.6025mg/L, Cu 4.159mg/L, Ni 0.2819mg/, Pb 0.4639mg/L and Zn 52.40 mg/L; the concentration of dioxin contained is as follows: 180.9ng/g, and the toxicity equivalent is 2.601 ng/g; the laboratory self-made mixed heavy metal waste water, main pollutant concentration is respectively: cd: 50mg/L, Cr: 50mg/L, Ni: 50mg/L, Cu: 50mg/L, Pb: 50mg/L, Zn: 50mg/L, pH about 5.
The treatment method comprises the following steps: the main flow is detailed in FIG. 1. The garbage to be treated is incinerated, fly ash is washed for standby, and then 1kg of fly ash and 0.1mol of Na are added2HPO4And 2L of electroplating wastewater are respectively added into a closed container to be uniformly mixed, the mixture is treated by microwave for 90 minutes at the temperature of 220 ℃, then liquid-solid separation is carried out, and a harmless product (adsorbent) can be obtained after drying.
The analysis process comprises the following steps: measuring the leaching concentration of heavy metals in the dried solid product by adopting a solid waste leaching toxicity leaching method, namely an acetic acid buffer solution method (HJ/T300-2007); determining the concentration of heavy metal in the wastewater after the co-treatment; analyzing the content of dioxin by adopting a high-resolution gas chromatography/high-resolution mass spectrometer (HRGC/MS); and (3) carrying out cation exchange amount detection and heavy metal adsorption experimental study on the solid product.
And (3) measuring results: heavy metal leaching results of solid product: cd 0.0785mg/L, Cu 1.208mg/L, Ni 0.1423mg/L, Pb 0.0614mg/L, Zn 1.635mg/L, dioxin toxicity equivalent: 0.161 ng/g; cation exchange amount: 0.804 meq/g; concentration of pollutants after co-treatment of wastewater: cd: 0.3157mg/L, Cr: 0.2485mg/L, Ni: 0.8895mg/L, Cu: 0.0927mg/L, Pb: 0.0872mg/L, Zn: 0.2824 mg/L.
And (4) conclusion: under the condition, the heavy metal stabilization degree is extremely high; the degradation rate of the dioxin exceeds 93 percent, so that the toxicity of the dioxin is far lower than the requirement of the domestic garbage landfill standard; the adsorbability of the treated product is improved by more than 30 times; the total removal effect of the ions in the wastewater is higher than 99 percent, and the actual engineering requirements are completely met.
Claims (5)
1. A harmless co-processing method for applying a microwave hydrothermal method to fly ash and electroplating wastewater is characterized by comprising the following steps:
1) carrying out water washing pretreatment on the fly ash;
2) detecting the content of cyanide in the electroplating wastewater, if the content of cyanide in the electroplating wastewater is higher than 0.5mg/L, adding hydrogen peroxide into the electroplating wastewater containing cyanide for oxidation treatment, otherwise, not needing treatment;
3) adding electroplating wastewater into the pretreated fly ash according to the solid-to-liquid ratio of 1 (1-2) kg/L, then adding an additive, and uniformly stirring to obtain mortar; the electroplating wastewater contains heavy metal ions;
4) pouring the mortar into a closed container for microwave heating, and reacting at the temperature of 200 ℃ and 250 ℃ for 1-2 h; and (3) performing solid-liquid separation on the product after microwave treatment, discharging waste liquid as household garbage, and drying the waste solid to reuse as an adsorbent.
2. The method for harmless co-processing of fly ash and electroplating wastewater according to claim 1, wherein the additive is soluble phosphate, and the amount of soluble phosphate added per kg of fly ash is 0.05-0.1 mol.
3. The method for harmless co-processing of fly ash and electroplating wastewater according to claim 1, wherein the microwave heating temperature is 210-230 ℃.
4. The method for harmless co-processing of fly ash and electroplating wastewater according to claim 1, wherein the microwave heating time is 60-90 min.
5. The harmless co-processing method for applying the microwave hydrothermal method to fly ash and electroplating wastewater according to claim 1, wherein heavy metal ions contained in the electroplating wastewater are one or more of Pb ions, Cu ions, Cr ions, Cd ions, Ni ions and Zn ions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526765A (en) * | 2021-06-24 | 2021-10-22 | 东江环保股份有限公司 | Harmless co-disposal method for fly ash and electroplating wastewater |
| CN116813374A (en) * | 2022-12-14 | 2023-09-29 | 张锦彬 | Ceramic manufactured by fly ash of garbage power plant |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526765A (en) * | 2021-06-24 | 2021-10-22 | 东江环保股份有限公司 | Harmless co-disposal method for fly ash and electroplating wastewater |
| CN116813374A (en) * | 2022-12-14 | 2023-09-29 | 张锦彬 | Ceramic manufactured by fly ash of garbage power plant |
| CN116813374B (en) * | 2022-12-14 | 2024-04-09 | 张锦彬 | Ceramic manufactured by fly ash of garbage power plant |
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