CN110586612B - Harmless treatment method for co-processing incineration fly ash by using chromium slag - Google Patents
Harmless treatment method for co-processing incineration fly ash by using chromium slag Download PDFInfo
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- CN110586612B CN110586612B CN201910790837.3A CN201910790837A CN110586612B CN 110586612 B CN110586612 B CN 110586612B CN 201910790837 A CN201910790837 A CN 201910790837A CN 110586612 B CN110586612 B CN 110586612B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Abstract
The invention discloses a harmless treatment method for treating incineration fly ash by using chromium slag in a synergistic manner, which comprises the following steps: pretreating fly ash; taking pretreated fly ash, chromium slag, waste glass powder and additives as raw materials; the raw materials are crushed, mixed evenly, roasted, cooled and cooled to obtain the molten glass body. The invention can not only avoid the pollution problem caused by the mass stockpiling of the chromium slag, realize the harmless treatment of the incineration fly ash, but also synchronously realize the reclamation of the chromium slag and the fly ash; the leaching rate index of the finished product is lower than the leaching toxicity identification standard value in the leaching toxicity identification standard (GB 5085.3-2007); short process flow and wide raw material adaptability, and realizes the dual purposes of economic benefit and environmental protection.
Description
Technical Field
The invention relates to the technical field of hazardous waste disposal and artificial building materials, in particular to a harmless treatment method for co-disposing incineration fly ash by utilizing chromium slag, which is a novel interdisciplinary method.
Background
The chromium slag is industrial waste slag generated in the process of producing metal chromium and chromium salt. The chromium slag contains hexavalent chromium with great toxicity, and the hexavalent chromium compound has strong oxidizability and great toxicity to human health, and is one of the internationally recognized dangerous solid wastes. The large amount of chromium slag stacking not only causes the occupation of land resources, but also causes serious pollution to underground water and soil in the stacking area. At present, the treatment method of the chromium slag mainly comprises several technologies of chromium slag replacing dolomite for sintering ironmaking, cement mineralizer, dry-wet detoxification, glass colorant and the like, and although the treatment technologies can relieve the pollution of the chromium slag to a greater extent, the treatment technologies have certain limitations in practical application.
The domestic garbage can generate a large amount of fly ash in the incineration process, and the amount of the fly ash accounts for 3% -5% of the total amount of the incineration garbage. Since the fly ash contains toxic and harmful heavy metals such as Hg, Zn, Pb, Cd, Cu and the like and highly toxic organic matters such as dioxin and the like, the fly ash is definitely classified as HW 18-type hazardous waste by the national hazardous waste record and needs strict management and safe disposal. At present, the safe disposal method of fly ash mainly comprises the technologies of cement solidification, chemical agent stabilization, melting solidification and the like. The cement solidification and chemical agent treatment are most widely applied at present, but the stabilized fly ash needs to enter a landfill site for landfill disposal, occupies land resources and has long-term environmental exposure risk.
Disclosure of Invention
Aiming at the defects in the problems, the invention provides a harmless treatment method for treating incineration fly ash by using chromium slag; the method can avoid the pollution problem caused by the stacking of a large amount of chromium slag, realize the harmless treatment of incineration fly ash, synchronously realize the reclamation of the chromium slag and the fly ash, has short process flow and wide raw material adaptability, and realizes the dual purposes of economic benefit and environmental protection.
The invention discloses a harmless treatment method for treating incineration fly ash by using chromium slag in a synergistic manner, which comprises the following steps:
pretreating fly ash;
taking pretreated fly ash, chromium slag, waste glass powder and additives as raw materials;
the raw materials are crushed, mixed, uniformly mixed, roasted, cooled and cooled to obtain the molten glass body.
As a further improvement of the invention, the pretreatment method of the fly ash comprises the following steps:
washing with water by a washing desalting method to ensure that the content of chloride ions in the fly ash after washing with water is less than or equal to 2 percent;
and dehydrating and drying the washed fly ash to ensure that the water content in the dried fly ash is lower than 5 percent.
As a further improvement of the invention, the crushing method comprises the following steps:
crushing the pretreated fly ash, chromium slag, waste glass powder or additive to the granularity of less than 5 mm.
As a further improvement of the invention, the blending method comprises the following steps:
firstly, dry mixing the mixed materials after the ingredients are mixed, wherein the dry mixing time is not less than 3 min; adding water, and mixing for at least 5 min.
As a further improvement of the invention, the roasting method comprises the following steps:
uniformly distributing the uniformly mixed materials in roasting equipment, introducing a reducing agent, roasting in a reducing atmosphere at the roasting temperature of 1100-1600 ℃, and softening, melting and bonding different minerals into blocks in a high-temperature reducing atmosphere.
As a further improvement of the invention, the roasting equipment is selected from a rotary kiln, a vertical furnace kiln, an electric furnace or a sintering machine.
As a further improvement of the invention, the reducing agent comprises one or more of a solid reducing agent comprising one or more of pulverized coal and coke and a gaseous reducing agent comprising one or more of blast furnace gas, coke oven gas, mixed gas and water gas.
As a further improvement of the invention, the cooling method comprises the following steps:
discharging the roasted molten material into a water quenching water tank from a slag discharge port, and cooling under a water seal cooling condition, wherein the water quenching temperature is not higher than 30 ℃.
As a further improvement of the invention, the waste glass powder is various recycled waste glass, and is used as a raw material after being crushed and ground.
As a further improvement of the invention, the additive comprises one or more of dolomite, quartz sand, sodium carbonate and calcium-free chromium slag.
Compared with the prior art, the invention has the beneficial effects that:
1. the harmless treatment method provided by the invention has the advantages that the needed raw materials are mostly hazardous waste and general waste, the co-treatment method of co-treating incineration fly ash by using chromium slag is adopted, the cost is low, and the environmental hazard is reduced to the greatest extent;
2. the harmless treatment method provided by the invention has wide raw material adaptability, and can treat various dangerous waste chromium slag, chromium-containing waste slag, household garbage incineration fly ash, dangerous waste incineration fly ash and other dangerous waste incineration fly ash;
3. the harmless treatment method provided by the invention can synchronously realize the reclamation of the fly ash and the chromium slag, converts the dangerous waste to be treated into high-quality building material raw materials, and relieves the current situation of resource exhaustion of the high-quality building material raw materials;
4. the harmless treatment method provided by the invention has extremely low raw material cost, and greatly saves the production cost of finished products while realizing the aim of treating wastes with processes of wastes against one another;
5. according to the harmless treatment method provided by the invention, the leaching rate index of the prepared finished product is lower than the leaching toxicity identification standard value in the leaching toxicity identification standard (GB 5085.3-2007).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are 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.
The analysis of the chromium slag and the incineration fly ash shows that:
the main component in the chromium slag is Fe2O3、Al2O3、CaO、MgO、SiO2And the fly ash contains higher mass fractions of calcium, aluminum and silicon oxides, and the two wastes can synergistically replace or partially replace the building material. Meanwhile, in the high-temperature treatment process, hexavalent chromium in the chromium slag is reduced into trivalent chromium, and main pollution components such as heavy metal, dioxin and the like in the fly ash are treated, so that the effect of harmless treatment is achieved.
The invention provides a harmless treatment method for treating incineration fly ash by using chromium slag in a synergistic manner, which comprises the following steps:
pretreating fly ash, and taking pretreated fly ash, chromium slag, waste glass powder and additives as raw materials; the raw materials are crushed, mixed evenly, roasted, cooled and cooled to obtain the molten glass body.
The method specifically comprises the following steps:
step 1, pretreating fly ash: washing with water by a washing desalting method to ensure that the content of chloride ions in the fly ash after washing with water is less than or equal to 2 percent; and dehydrating and drying the washed fly ash to ensure that the water content in the dried fly ash is lower than 5 percent.
And 2, selecting the pretreated fly ash, the chromium slag, the waste glass powder and the additive as raw materials for harmless treatment of the chromium slag and the incineration fly ash. Wherein the content of the first and second substances,
the waste glass powder is various recycled waste glass, and is used as a raw material after being crushed and ground;
the additive comprises one or more of dolomite, quartz sand, sodium carbonate and calcium-free chromium slag; wherein, the dolomite, the quartz sand, the sodium carbonate and the calcium-free chromium slag are selectively added according to the element proportion condition of the mixture.
Step 3, crushing the waste materials before uniformly mixing, grinding the materials to a sufficient particle size, wherein the particle size is preferably less than 5mm, and crushing and grinding again after sieving the materials with an overlarge particle size;
step 4, in order to obtain a roasted material with stable chemical components and physical properties so as to meet the requirement of the high-strength refractory material, the finely ground pretreated fly ash, chromium slag, waste glass powder and additives are mixed into various materials according to a certain proportion by adopting a mass mixing method to form a mixture;
step 5, in order to make the mixture components uniform and have proper moisture, uniform mixing granularity and porosity so as to achieve the optimal roasting atmosphere, dry mixing is firstly carried out on the mixture, the dry mixing time is not less than 3min, then proper moisture is added, secondary uniform mixing is carried out, and the uniform mixing time is not less than 5 min;
and 6, uniformly distributing the uniformly mixed materials in roasting equipment, introducing a reducing agent, roasting in a reducing atmosphere, wherein the roasting temperature is 1100-1600 ℃, and different minerals are softened, melted and bonded into blocks in a high-temperature reducing atmosphere. Dioxin in the fly ash is completely decomposed in the high-temperature melting process, and heavy metals are chemically solidified into a melting material, so that the harmless treatment of the fly ash is realized; wherein:
the roasting equipment can be selected from smelting equipment such as a rotary kiln, a vertical furnace, an electric furnace, a sintering machine and the like;
the reducing agent comprises a solid reducing agent and a gas reducing agent, wherein the solid reducing agent such as powdered coal and coke can be added by adopting an internal mixing mode and an external mixing and refining mode, the gas reducing agent can be selected from blast furnace gas, coke oven gas, mixed gas, water gas and the like, and heat and reducing atmosphere are provided in the roasting stage.
And 7, after the materials are heated to a molten state, discharging the materials into a water quenching water tank from a slag discharge port, cooling the materials under a water seal cooling condition to prevent reduced hexavalent chromium from being oxidized again, wherein the water quenching temperature is not higher than 30 ℃, and a glass body is formed by water quenching and quenching, even if a very small amount of undetoxic harmful ingredients are sealed in crystal lattices of the glass body and are difficult to dissolve out, and the glass body is sent to a cement plant or a building material plant for comprehensive utilization.
Example 1:
the embodiment provides a harmless treatment method for co-processing incineration fly ash by using chromium slag, which comprises the following steps:
1) preparing raw materials: the raw materials required by the preparation method comprise pretreated fly ash, chromium slag, waste glass powder, additives and reducing coal. The waste materials are crushed before being mixed uniformly, the materials are ground to a sufficient size fraction, the granularity is preferably less than 5mm, and the materials are crushed and ground again after being screened to have overlarge granularity.
The hazardous waste chromium slag stored in a certain chromium salt production enterprise is used as a raw material, and the main chemical components are as follows:
9.57 percent of silicon dioxide, 4.58 percent of aluminum oxide, 31.11 percent of calcium oxide, 21.79 percent of magnesium oxide, 8.13 percent of ferric oxide and chromium oxide (Cr)2O3) 3.44%, dichromium hexaoxide (Cr)2O6) 0.5% and sodium dichromate (Na)2Cr2O7) About 1%, etc. The chromium slag contains periclase (MgO) and calcium silicate (2 CaO. SiO) as main minerals2) Brucite (4 CaO. Al)2O3·Fe2O3) And 1 to 10 percent of residual chromite and the like.
The fly ash from incineration of certain household garbage is used as a raw material, and the main chemical components are as follows:
20.5 percent of silicon dioxide, 5.8 percent of aluminum oxide, 35.8 percent of calcium oxide, 2.1 percent of magnesium oxide, 3.2 percent of ferric oxide, 3.7 percent of sodium oxide, 11.4 percent of chlorine, 1464mg/Kg of lead, 4179.5mg/Kg of zinc, and the like.
The pretreatment process of the fly ash comprises the following steps: and (3) washing and desalting to obtain a washed fly ash raw material with the chlorine content of 1.5%, and drying the washed fly ash raw material in a vacuum drying oven until the moisture content is 3% to obtain the pretreated fly ash.
2) Preparing materials: in order to obtain a roasting material with stable chemical components and physical properties to meet the requirements of high-strength refractory raw materials, various materials are added into levigated pretreated fly ash, chromium slag, waste glass powder and additives by adopting a mass proportioning method to form a mixture, wherein the fly ash, the chromium slag, the waste glass powder, the calcium-free chromium slag and the sodium carbonate are mixed according to the mass ratio of 1: 0.2: 0.2: 0.1.
3) Uniformly mixing: in order to ensure that the mixture has uniform components and proper moisture, uniform mixing granularity and porosity so as to achieve the optimal roasting atmosphere, the mixture is dry-mixed for 3min, then proper moisture is added, and secondary uniform mixing is carried out for 5 min;
4) roasting: uniformly distributing the uniformly mixed material in roasting equipment, paving the bottom by adding 50% reducing coal, roasting in reducing atmosphere, preheating for 5min at 800 ℃, heating for 30min at 1350 ℃ for melting, and softening, melting and bonding different minerals into blocks in high-temperature reducing atmosphere. .
5) And (3) cooling: after the material is heated to a molten state, the material is discharged into a water quenching water tank from a slag discharge port, and is cooled under the water seal cooling condition, so that reduced hexavalent chromium is prevented from being oxidized again, the water quenching temperature is not higher than 30 ℃, a glass body is formed by water quenching and quenching, even a very small amount of harmful components which are not detoxified are sealed in crystal lattices of the glass body and are difficult to dissolve out, and the glass body is sent to a cement plant or a building material plant for comprehensive utilization.
The obtained vitrified solid was subjected to a toxicity leaching experiment, and the results are shown in table 1.
TABLE 1 toxicity Leaching assay results
| Element name | As | Pb | Cd | Hg | Zn | Cu | F |
| Content (mg/L) | Not detected out | 1.10 | 0.17 | 0.01 | 1.80 | 0.15 | 0.02 |
Example 2:
the embodiment provides a harmless treatment method for co-processing incineration fly ash by using chromium slag, which comprises the following steps:
1) preparing raw materials: the raw materials required by the preparation method comprise pretreated fly ash, chromium slag, waste glass powder, additives and reducing coal. The waste materials are crushed before being mixed uniformly, the materials are ground to a sufficient size fraction, the granularity is preferably less than 5mm, and the materials are crushed and ground again after being screened to have overlarge granularity.
The hazardous waste chromium slag stored in a certain chromium salt production enterprise is used as a raw material, and the main chemical components are as follows:
9.57 percent of silicon dioxide, 4.58 percent of aluminum oxide, 31.11 percent of calcium oxide, 21.79 percent of magnesium oxide, 8.13 percent of ferric oxide and chromium oxide (Cr)2O3) 3.44%, dichromium hexaoxide (Cr)2O6) 0.5% and sodium dichromate (Na)2Cr2O7) About 1%, etc. The chromium slag contains periclase (MgO) and calcium silicate (2 CaO. SiO) as main minerals2) Brucite (4 CaO. Al)2O3·Fe2O3) And 1 to 10 percent of residual chromite and the like.
The fly ash from incineration of certain household garbage is used as a raw material, and the main chemical components are as follows:
20.5 percent of silicon dioxide, 5.8 percent of aluminum oxide, 35.8 percent of calcium oxide, 2.1 percent of magnesium oxide, 3.2 percent of ferric oxide, 3.7 percent of sodium oxide, 11.4 percent of chlorine, 1464mg/Kg of lead, 4179.5mg/Kg of zinc, and the like.
The pretreatment process of the fly ash comprises the following steps: and (3) washing and desalting to obtain a washed fly ash raw material with the chlorine content of 1.5%, and drying the washed fly ash raw material in a vacuum drying oven until the moisture content is 3% to obtain the pretreated fly ash.
2) Preparing materials: in order to obtain a roasting material with stable chemical components and physical properties to meet the requirements of high-strength refractory raw materials, various materials are added into levigated pretreated fly ash, chromium slag, waste glass powder and additives by adopting a mass proportioning method to form a mixture, wherein the fly ash, the chromium slag, the waste glass powder, the calcium-free chromium slag and the sodium carbonate are mixed according to the mass ratio of 1: 0.2: 0.4: 0.1.
3) Uniformly mixing: in order to ensure that the mixture has uniform components and proper moisture, uniform mixing granularity and porosity so as to achieve the optimal roasting atmosphere, the mixture is dry-mixed for 3min, then proper moisture is added, and secondary uniform mixing is carried out for 5 min;
4) roasting: uniformly distributing the uniformly mixed material in roasting equipment, paving the bottom by adding 50% reducing coal, roasting in reducing atmosphere, preheating for 5min at 800 ℃, heating for 30min at 1350 ℃ for melting, and softening, melting and bonding different minerals into blocks in high-temperature reducing atmosphere. .
5) And (3) cooling: after the material is heated to a molten state, the material is discharged into a water quenching water tank from a slag discharge port, and is cooled under the water seal cooling condition, so that reduced hexavalent chromium is prevented from being oxidized again, the water quenching temperature is not higher than 30 ℃, a glass body is formed by water quenching and quenching, even a very small amount of harmful components which are not detoxified are sealed in crystal lattices of the glass body and are difficult to dissolve out, and the glass body is sent to a cement plant or a building material plant for comprehensive utilization.
The obtained vitrified solid was subjected to a toxicity leaching experiment, and the results are shown in table 2.
TABLE 2 toxicity leach-out analysis results
| Element name | As | Pb | Cd | Hg | Zn | Cu | F |
| Content (mg/L) | Not detected out | 0.87 | 0.08 | Not detected out | 0.56 | Not detected out | Not detected out |
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A harmless treatment method for treating incineration fly ash by using chromium slag in a synergistic manner is characterized by comprising the following steps:
pretreating fly ash; wherein, the water washing desalination method is adopted for water washing, so that the content of chloride ions in the fly ash after water washing is less than or equal to 2 percent; dehydrating and drying the washed fly ash to ensure that the water content in the dried fly ash is lower than 5 percent;
taking pretreated fly ash, calcium-containing chromium slag, waste glass powder and additives as raw materials; wherein the additive is sodium carbonate and calcium-free chromium slag;
crushing, burdening, uniformly mixing, roasting and cooling the raw materials to obtain a molten glass body; wherein the content of the first and second substances,
the uniformly mixing method comprises the following steps: firstly, dry mixing the mixed materials after the ingredients are mixed, wherein the dry mixing time is not less than 3 min; adding water, and mixing for at least 5 min;
the roasting method comprises the following steps: uniformly distributing the uniformly mixed material in roasting equipment, paving the bottom of the uniformly mixed material with 50% reducing coal, roasting in reducing atmosphere, preheating for 5min at 800 ℃, heating for 30min at 1350 ℃ for melting, and softening, melting and bonding different minerals into blocks in high-temperature reducing atmosphere;
the cooling method comprises the following steps: discharging the roasted molten material into a water quenching water tank from a slag discharge port, and cooling under a water seal cooling condition, wherein the water quenching temperature is not higher than 30 ℃.
2. A method of detoxification treatment according to claim 1, wherein the crushing method comprises:
crushing the pretreated fly ash, the calcium-containing chromium slag, the waste glass powder or the additive to the granularity of less than 5 mm.
3. A method according to claim 1, wherein the roasting apparatus is selected from a rotary kiln, a vertical kiln, an electric furnace, and a sintering machine.
4. A harmless treatment method according to claim 1, wherein the waste glass powder is various types of waste glass recovered, and is used as a raw material after being crushed and ground.
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| CN113958959B (en) * | 2021-11-12 | 2024-03-26 | 光大环保技术研究院（深圳）有限公司 | Method for controlling dioxin emission in fly ash plasma melting process |
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| 旋风炉掺烧铬渣污染物排放特性分析;杨晓东;《环境工程》;20180422;第36卷(第4期);第113-116页 * |
| 铬渣无害化处理技术研究进展;陆清萍;《化工环保》;20110815;第31卷(第4期);第318-322页 * |
| 高钙铬渣及其解毒后可溶六价铬含量分析方法研究;王天贵等;《无机盐工业》;20120410;第44卷(第4期);第1-4页 * |
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