CN114031250B - Method for hydrothermal treatment of domestic sludge by using zero-valent iron and fly ash - Google Patents
Method for hydrothermal treatment of domestic sludge by using zero-valent iron and fly ash Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F11/00—Treatment of sludge; Devices therefor
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- 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
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Abstract
The invention provides a method for hydrothermally treating domestic sludge by using zero-valent iron and fly ash, which comprises the following steps: s1, mixing the household garbage incineration fly ash with zero-valent iron to obtain a first mixed material; s2, mixing the first mixed material with domestic sludge to obtain a second mixed material; wherein the water content of the domestic sludge is not less than 50%; s3, carrying out hydrothermal treatment and solid-liquid separation treatment on the second mixed material in sequence to obtain a solid product and treated wastewater; subjecting the solid product to magnetic separation, a magnetic solid product and a non-magnetic solid product. The method can remove organic matters and adsorb heavy metals, can reduce the leaching toxicity of the product, has simple process, low cost, no secondary pollution and definite subsequent application, achieves the effect of treating wastes with processes of wastes against one another, and has higher social benefit and economic benefit.
Description
Technical Field
The invention relates to treatment of domestic sludge, in particular to a method for treating domestic sludge by using zero-valent iron and fly ash in a hydrothermal mode.
Background
Along with the continuous improvement of the urbanization level of China, the urban area is larger and larger, the construction of municipal sewage treatment facilities is developed at a high speed, and the discharge amount and the treatment rate of sewage are improved continuously. However, a large amount of municipal sludge is generated in the sewage treatment process, the annual output of the sludge in China is over 3000 ten thousand tons as soon as the water content is 80%, the annual output is increased year by year, in 2020, 6000 ten thousand tons are broken through, and the damage to the environment is very serious due to the unique physicochemical properties of the sludge, if the sludge is not properly treated and disposed. The main source of the sludge of the sewage plant is the product of the purification process of domestic sewage, municipal sewage and the like of residents, and the sludge is different from the soil sludge such as the sludge of the water plant and the like, the content of organic matters is higher, generally accounts for more than 50 percent of the dry basis content, and simultaneously contains a large amount of nutrient substances such as nitrogen, phosphorus and the like; as the sewage plant also receives some industrial wastewater, the sludge also contains a certain proportion of heavy metal ions and chemical substances, in particular contains a certain amount of harmful chemical substances, such as adsorbable organic halogen, anion synthetic detergent, polychlorinated biphenyl and the like, and a large amount of pathogenic microorganisms. Therefore, the municipal sludge treatment problem is increasingly prominent and the situation is very severe.
At present, the common processes for sludge treatment are as follows: mechanical dehydration is carried out on municipal sludge firstly, the water content of the municipal sludge is reduced, and then drying is carried out through drying equipment. Although the process can greatly reduce the energy consumption in the drying process, the process still has at least the following problems:
1. lime and ferric trichloride or polyacrylamide are generally used for conditioning the sludge in the mechanical dehydration stage, the dosage of the medicament is large (about 30 percent of the weight of the absolutely dry sludge), a large amount of resources are consumed, more impurities are introduced into the sludge, and the resource utilization rate of the dried sludge is low;
2. the sludge conditioned by polyacrylamide is difficult to dehydrate, has poor air permeability, is not beneficial to later drying, and has high cost.
In view of the above, there is a need to provide a method for hydrothermally treating domestic sludge by using zero-valent iron in combination with fly ash, so as to solve or at least alleviate the above-mentioned disadvantages of high treatment cost, low resource availability, and difficult treatment process.
Disclosure of Invention
The invention mainly aims to provide a method for hydrothermally treating domestic sludge by using zero-valent iron and fly ash, and aims to solve the technical problems of high treatment cost, low resource utilization rate and difficult treatment process.
In order to realize the aim, the invention provides a method for hydrothermally treating domestic sludge by using zero-valent iron and fly ash, which comprises the following steps:
s1, mixing the household garbage incineration fly ash with zero-valent iron to obtain a first mixed material;
s2, mixing the first mixed material with domestic sludge to obtain a second mixed material; wherein the water content of the domestic sludge is not less than 50%;
s3, carrying out hydrothermal treatment and solid-liquid separation treatment on the second mixed material in sequence to obtain a solid product and treated wastewater.
Further, the step S3 further includes: and carrying out magnetic separation on the solid product to obtain a magnetic solid product and a non-magnetic solid product.
Further, the household garbage incineration fly ash comprises chlorine and heavy metals.
Further, the heavy metals in the household garbage incineration fly ash comprise arsenic, mercury, chromium, lead, uranium, manganese, copper, nickel and zinc.
Further, the zero-valent iron is strongly impacted in an ultrasonic mechanical ball mill by a mechanical ball milling method, and the metallic iron powder is transformed into a material containing a large amount of Fe by solid state reaction, fracture, grinding and stirring0The reaction site.
Further, in the step S1, the mass ratio of the household garbage incineration fly ash to the zero-valent iron is 5: 1-20: 1.
Further, the domestic sludge comprises organic matters and heavy metals.
Further, the heavy metals in the domestic sludge include copper, chromium and cadmium.
Further, the water content of the domestic sludge is 70-80%.
Further, in the step S2, the mass ratio of the first mixed material to the domestic sludge is 1: 10-1: 15.
Further, in the step S3, the temperature of the hydrothermal treatment is 150-180 ℃, and the duration of the hydrothermal treatment is 6-12 h.
The main principle of the invention comprises: the municipal sludge raw slag has water content of more than 50 percent, complex components and high salt content, and the sludge contains thousands of pathogens in polluted wastewater, and contains a large amount of heavy metals such as copper, chromium, cadmium and the like, wherein the metals mostly exist in an amorphous state or in states of calcium sulfate dihydrate, calcium sulfate hemihydrate, metal oxides and the like. The fly ash also contains heavy metals such As Pb, Zn, Cu, Cr, Cd, Ni, As, Hg and the like and highly toxic substances such As dioxin, polycyclic aromatic hydrocarbon and the like, and simultaneously contains a large amount of chloride ions.
In the step S1, the fly ash from incineration is mixed with the zero-valent iron pesticide, so that the fly ash particles are fully contacted with the zero-valent iron pesticide; when the domestic sludge with high water content in the step S2 and the mixed product in the step S1 are stirred, mixed uniformly and subjected to the hydrothermal treatment in the step S3, the chlorine salt and the Cl serving as the initiators of the corrosion reaction of zero-valent iron are firstly contained in the mixed solution-It can easily enter the zero-valent iron oxide layer and disperse the oxide layer to increase its permeability. Cl-Is adsorbed into the oxide layer together with dissolved oxygen and OH-Constitute a competition, which favors the hydration reaction of the metal ions and promotes the entry of the metal ions into solution, electrochemically, adsorbed Cl-The exchange current of the anode is increased. By Cl-Cracks and pits appear on the modified surface, the surface of the zero-valent iron is activated by anodic corrosion of the pits, and the rate of organic matter degradation of the zero-valent iron can be accelerated by pit corrosion. In the subsequent standing process, a large amount of metal ions and organic matters in the raw slag are adsorbed on zero-valent iron, so that the heavy metal ions and part of the organic matters are removed through the promotion effect of chloride ions in the fly ash by the magnetic separation, and the purpose of treating wastes with processes of wastes against one another is achieved.
Compared with the prior art, the invention has the following advantages:
the invention provides a method for treating domestic sludge by using zero-valent iron and fly ash in a synergistic manner, which is characterized in that municipal sludge with high organic matters is treated by using waste incineration fly ash and zero-valent iron together, and the chlorine ions in the fly ash can promote the zero-valent iron to degrade organic matters and adsorb heavy metals by combining with a hydrothermal reaction, so that the aims of detoxifying hazardous wastes and separating the organic matters are fulfilled. In addition, the treatment method has the advantages of simple process, low cost, no secondary pollution and definite subsequent application, achieves the effect of treating wastes with processes of wastes against one another, and has higher social and economic benefits.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is an XRD pattern of fly ash in example 1 of the present invention;
FIG. 2 is an XRD pattern of a magnetically separated non-magnetic solid product of example 1 of the present invention;
fig. 3 is an XRD pattern of the magnetically separated magnetic solid product of example 1 of the present invention.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that all the directional indicators (such as the upper and lower … …) in the embodiment of the present invention are only used to explain the relative position relationship, movement, etc. of the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
The invention provides a method for hydrothermally treating domestic sludge by using zero-valent iron and fly ash, which comprises the following steps:
s1, mixing the household garbage incineration fly ash with zero-valent iron to obtain a first mixed material; further, the zero-valent iron used in the present invention is a mechanical ball milling method in which metallic iron powder is transformed, fractured, ground and stirred by solid state reaction to contain a large amount of Fe0The mass ratio of the substance at the reaction site, the domestic garbage incineration fly ash and the zero-valent iron can be 5: 1-20: 1.
S2, mixing the first mixed material with domestic sludge to obtain a second mixed material; further, the mass ratio of the first mixed material to the domestic sludge can be 1: 10-1: 15.
Wherein, in order to ensure the reaction, the domestic sludge needs to have high water content (with flowing water), and the water content of the domestic sludge is not less than 50% in general; preferably, the water content of the domestic sludge is 70-80%, and specifically 80%. Based on the above, the invention not only does not need to consider the problem that the domestic sludge is difficult to dehydrate due to high water content, but also can fully treat the domestic sludge with high water content.
S3, carrying out hydrothermal treatment and solid-liquid separation treatment on the second mixed material in sequence to obtain a solid product and treated wastewater. In addition, the solid product is magnetically separated, and a magnetic solid product and a non-magnetic solid product can be obtained.
Wherein, the treated wastewater belongs to supernatant, contains less impurities and can be directly discharged; although the solid product is a bottom sediment and contains a large amount of heavy metals in the raw sludge and the raw fly ash, the test proves that the leaching toxicity is low, the environmental impact is not needed to be worried about, and the organic matters contained in the solid product are reduced because part of the organic matters are degraded.
As an illustration of further processing, after the solid product is subjected to magnetic separation, a large amount of heavy metals and a part of organic matters are removed from the non-magnetic solid product, so that the influence of the non-magnetic solid product on the environment is further reduced; in addition, compared with the complexity of the domestic sludge and the solid product, for the magnetic solid product and the non-magnetic solid product, the heavy metal adsorbed in the magnetic solid product can be desorbed, enriched, recycled and reused, and the non-magnetic solid product can be landfilled or further optimized to be used as a building material.
As an illustration of the hydrothermal treatment, the hydrothermal treatment is carried out in a hydrothermal reaction kettle, the temperature of the hydrothermal treatment is 150-180 ℃, and the duration of the hydrothermal treatment is 6-12 h.
It is understood that the household garbage incineration fly ash belongs to CaO-CaCl2-CaSO4-SiO2And (4) preparing the system. Because the content of chloride and chlorine-containing organic matters in municipal solid waste in China is high, acidic gases such As HCl and the like can be generated in an incineration system, and therefore, a large amount of lime needs to be sprayed into a flue gas purification system to neutralize the acidic gases in tail gas, so that the fly ash has high chlorine content and strong alkalinity, meanwhile, the fly ash also contains heavy metals such As Pb, Zn, Cu, Cr, Cd, Ni, As, Hg and the like and highly toxic substances such As dioxin, polycyclic aromatic hydrocarbon and the like, the danger is extremely high, and the generation amount is huge. At present, aiming at waste incineration fly ash, the prior treatment technology mainly adopts stabilization/landfill after solidification, and has the problems of large capacity-increasing ratio, more occupied land, poor stability and the like. Therefore, the combination of the synergy of the domestic waste incineration fly ash and the domestic sludge can not only complete the effective treatment of the domestic sludge, but also carry out deep synchronous treatment on the domestic waste incineration fly ash。
The fly ash from incineration of household garbage comprises heavy metals and chlorine, rare earth elements, fluorine and other elements, wherein the heavy metals comprise arsenic, mercury, chromium, lead, uranium, manganese, copper, nickel, zinc and the like. It should be noted that the present invention is only illustrative of some of the substances in the fly ash from incineration of household garbage, and does not represent all the substances contained in the fly ash from incineration of household garbage.
The introduction of the domestic sludge has been described in the background of the invention, and the domestic sludge used in the invention is the same as the domestic sludge, and it should be described again that the domestic sludge is derived from municipal sludge and includes organic matter, heavy metals and the like as part of its components. The heavy metals in the domestic sludge comprise copper, chromium, cadmium and the like.
To facilitate a further understanding of the invention, reference will now be made to the following examples:
example 1
1. Mixing the household garbage incineration fly ash and zero-valent iron according to a mass ratio of 5:1 to obtain a first mixed material;
2. uniformly stirring and mixing the first mixed material and domestic sludge (municipal sludge) with the water content of 80% according to the mass ratio of 1:15 to obtain a second mixed material;
3. carrying out hydrothermal reaction on the second mixed material at 150 ℃ for 6 hours, standing, cooling and centrifugally separating after hydrothermal reaction to obtain a solid product; and carrying out magnetic separation on the solid product to obtain a magnetic solid product and a non-magnetic solid product.
4. The solid product is subjected to leaching toxicity test according to the national standard hazardous waste identification standard 'leaching toxicity identification GB 5085.3-2007', and then the amount of organic matters in the solid product (namely, the product which is not subjected to magnetic separation) is measured.
In this example, 2.5 g of fly ash from incineration of domestic waste and 45 g of domestic sludge with high organic content were treated.
Taking metallic lead as an example, the leaching toxicity of lead (Pb) in fly ash before treatment is 11.94 mg/L. After synergistic solidification, the leaching toxicity of lead (Pb) in the solid product is 0.9598mg/L < 5mg/L (hazardous waste identification standard leaching toxicity identification GB 5085.3-2007).
Further, it was determined that: after solid-liquid separation, the content of organic matters in the solid product is reduced by 30 percent, which shows that 30 percent of the organic matters are degraded.
In addition: the XRD patterns of the fly ash raw slag, the non-magnetic solid product and the magnetic solid product in this example are shown in fig. 1 to 3.
Example 2
1. Mixing the household garbage incineration fly ash and zero-valent iron according to a mass ratio of 20:1 to obtain a first mixed material;
2. uniformly stirring and mixing the first mixed material and domestic sludge (municipal sludge) with the water content of 80% according to the mass ratio of 1:15 to obtain a second mixed material;
3. carrying out hydrothermal reaction on the second mixed material at 150 ℃ for 6 hours, standing, cooling and centrifugally separating after hydrothermal reaction to obtain a solid product; and carrying out magnetic separation on the solid product to obtain a magnetic solid product and a non-magnetic solid product.
4. The solid product is subjected to leaching toxicity test according to a hazardous waste identification standard GB 5085.3-2007, and then the amount of organic matters in the solid product (i.e., the product which is not subjected to magnetic separation) is determined.
In this example, 2.5 g of fly ash from incineration of domestic waste and 45 g of domestic sludge with high organic content were treated.
Taking metallic lead as an example, the leaching toxicity of lead (Pb) in fly ash is 11.94mg/L before the treatment; after synergistic solidification, the leaching toxicity of lead (Pb) in the solid product is 1.2576mg/L < 5mg/L (hazardous waste identification standard leaching toxicity identification GB 5085.3-2007).
Further, it was determined that: the organic content in the solid product was reduced by 15%, indicating that 15% of the organic was degraded.
Example 3
1. Mixing the household garbage incineration fly ash and zero-valent iron according to a mass ratio of 5:1 to obtain a first mixed material;
2. uniformly stirring and mixing the first mixed material and domestic sludge (municipal sludge) with the water content of 80% according to the mass ratio of 1:10 to obtain a second mixed material;
3. carrying out hydrothermal reaction on the second mixed material at 150 ℃ for 6 hours, standing, cooling and centrifugally separating after hydrothermal reaction to obtain a solid product; and carrying out magnetic separation on the solid product to obtain a magnetic solid product and a non-magnetic solid product.
4. The solid product is subjected to leaching toxicity test according to a hazardous waste identification standard GB 5085.3-2007, and then the amount of organic matters in the solid product (i.e., the product which is not subjected to magnetic separation) is determined.
In this example, 2.5 g of fly ash from incineration of domestic waste and 25 g of domestic sludge with high organic content were treated.
Taking metallic lead as an example, the leaching toxicity of lead (Pb) in fly ash is 11.94mg/L before the treatment; after synergistic solidification, the leaching toxicity of lead (Pb) in the solid product is 1.0598mg/L < 5mg/L (hazardous waste identification standard leaching toxicity identification GB 5085.3-2007).
Further, it was determined that: the organic content in the solid product was reduced by 20%, indicating that 20% of the organic was degraded.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.
Claims (10)
1. A method for treating domestic sludge by using zero-valent iron and fly ash in a hydrothermal mode is characterized by comprising the following steps:
s1, mixing the household garbage incineration fly ash with zero-valent iron to obtain a first mixed material; wherein the zero-valent iron is derived from metal iron powder treated by a mechanical ball milling method;
s2, mixing the first mixed material with domestic sludge to obtain a second mixed material; wherein the water content of the domestic sludge is not less than 50%;
s3, carrying out hydrothermal treatment and solid-liquid separation treatment on the second mixed material in sequence to obtain a solid product and treated wastewater.
2. The method for the hydrothermal treatment of domestic sludge with zero-valent iron in combination with fly ash according to claim 1, wherein the step S3 further comprises: and carrying out magnetic separation on the solid product to obtain a magnetic solid product and a non-magnetic solid product.
3. The method for the hydrothermal treatment of domestic sludge by using zero-valent iron in combination with fly ash according to claim 1, wherein the fly ash from incineration of domestic garbage comprises chlorine and heavy metals.
4. The method for the hydrothermal treatment of domestic sludge by using zero-valent iron in combination with fly ash according to claim 3, wherein the heavy metals in the fly ash from incineration of domestic garbage include arsenic, mercury, chromium, lead, uranium, manganese, copper, nickel and zinc.
5. The method for hydrothermally treating domestic sludge with zero-valent iron in cooperation with fly ash according to claim 1, wherein in step S1, the mass ratio of the domestic waste incineration fly ash to the zero-valent iron is 5: 1-20: 1.
6. The method for the hydrothermal treatment of domestic sludge with zero-valent iron in combination with fly ash according to claim 1, wherein the domestic sludge comprises organic matter and heavy metals.
7. The method of claim 6, wherein the heavy metals in the domestic sludge include copper, chromium and cadmium.
8. The method for hydrothermally treating domestic sludge by using zero-valent iron and fly ash according to claim 1, wherein the water content of the domestic sludge is 70-80%.
9. The method for hydrothermally treating domestic sludge with zero-valent iron in cooperation with fly ash according to claim 1, wherein in step S2, the mass ratio of the first mixed material to the domestic sludge is 1:10 to 1: 15.
10. The method for hydrothermally treating domestic sludge with zero-valent iron in cooperation with fly ash according to any one of claims 1 to 9, wherein in step S3, the temperature of the hydrothermal treatment is 150 ℃ to 180 ℃, and the duration of the hydrothermal treatment is 6 to 12 hours.
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| CN103253757B (en) * | 2013-05-16 | 2014-04-02 | 同济大学 | Method for deep treatment of complex industrial wastewater by utilizing nano-zero-valent iron |
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