CN107252810A - A kind of method of heavy metal in melting and solidification incineration firing flying dust - Google Patents
A kind of method of heavy metal in melting and solidification incineration firing flying dust Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000007711 solidification Methods 0.000 title claims abstract description 22
- 230000008023 solidification Effects 0.000 title claims abstract description 22
- 238000002844 melting Methods 0.000 title claims abstract description 16
- 230000008018 melting Effects 0.000 title claims abstract description 16
- 239000000428 dust Substances 0.000 title claims description 7
- 238000010304 firing Methods 0.000 title claims 5
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 239000010881 fly ash Substances 0.000 abstract description 39
- 239000002699 waste material Substances 0.000 abstract description 29
- 238000002485 combustion reaction Methods 0.000 abstract description 28
- 238000002386 leaching Methods 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 11
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 229910052763 palladium Inorganic materials 0.000 abstract description 7
- 229910052793 cadmium Inorganic materials 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 5
- 239000010813 municipal solid waste Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000010668 complexation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- 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 NOT OTHERWISE PROVIDED FOR
- 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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Abstract
本发明公开了一种熔融固化垃圾燃烧飞灰中重金属的方法，属于固体废弃物利用及污染控制技术领域。该方法通过将垃圾飞灰与高炉瓦斯泥以9～1:1的比例混合加热到800到1200℃，保温0.5～3小时，最后得到熔融固化产物，按照国标对之进行As、Cd、Cr、Cu、Ni、Pd及Zn重金属浸出检测，结果表明：固化产物完全符合国家排放标准。与传统方法相比，本发明利用高炉瓦斯泥高温熔融固化垃圾燃烧飞灰中重金属，可有效的降低飞灰中重金属的浸出及环境污染，从而克服了现有固化重金属技术单纯依赖一次资源和化学试剂的局限，在降低垃圾燃烧飞灰重金属污染的同时，也为高炉瓦斯泥无害化和资源化利用提供了新途径。
The invention discloses a method for melting and solidifying garbage to burn heavy metals in fly ash, and belongs to the technical field of solid waste utilization and pollution control. The method is to mix garbage fly ash and blast furnace gas mud at a ratio of 9 to 1:1 and heat it to 800 to 1200°C, keep it warm for 0.5 to 3 hours, and finally obtain a molten and solidified product, which is subjected to As, Cd, Cr, The leaching test of Cu, Ni, Pd and Zn heavy metals shows that the cured products fully meet the national emission standards. Compared with the traditional method, the present invention utilizes high-temperature melting and solidification of blast furnace gas mud to solidify heavy metals in waste combustion fly ash, which can effectively reduce the leaching of heavy metals in fly ash and environmental pollution, thereby overcoming the existing technology of solidifying heavy metals that relies solely on primary resources and chemical The limitation of reagents not only reduces the pollution of heavy metals in fly ash of waste combustion, but also provides a new way for the harmless and resource utilization of blast furnace gas mud.
Description
技术领域technical field
本发明属于固体废弃物利用及污染控制技术领域，具体涉及一种以高炉瓦斯灰和垃圾燃烧飞灰为研究对象，混合后高温熔融降低重金属污染的一种方法。The invention belongs to the technical field of solid waste utilization and pollution control, and in particular relates to a method for reducing heavy metal pollution by taking blast furnace gas ash and waste combustion fly ash as research objects and melting at high temperature after mixing.
背景技术Background technique
垃圾焚烧飞灰中含有一定量的有害物质,特别是重金属,飞灰中含有,易飞散,挥发性元素如Cl、Pb、Cd、Zn、Sb、Se化合物及单体富集物,若未经处理直接排放,将会污染土壤和地下水,对环境造成危害。目前焚烧飞灰稳定化处理的方法主要有：常温固化处置技术，包括水泥固化法、沥青固化法和石灰固化法；化学结合处置技术，包括药剂稳定化技术、PH值调控技术和沉淀技术；高温熔融固化技术，包括烧结固化和熔融固化；以及其他一些如离子交换技术、疏水处理技术、超临界流体萃取技术和生物浸提等技术飞灰熔融固化的目的在于将大部分重金属固化在致密的熔渣晶格结构中,从而使重金属溶出的可能性大大降低,达到控制重金属污染的目的。但是依赖化学药剂控制重金属污染成本较高，而且有可能会产生二次污染，因此，寻找一条高效节能的且环保的方法是目前亟待解决的问题。Waste incineration fly ash contains a certain amount of harmful substances, especially heavy metals, which are easy to fly and disperse. Volatile elements such as Cl, Pb, Cd, Zn, Sb, Se compounds and monomer enrichments, if not Disposal of direct discharge will pollute soil and groundwater, causing harm to the environment. At present, the stabilization treatment methods of incineration fly ash mainly include: normal temperature solidification treatment technology, including cement solidification method, asphalt solidification method and lime solidification method; chemical combination disposal technology, including chemical stabilization technology, pH value control technology and precipitation technology; high temperature Melt solidification technology, including sinter solidification and melt solidification; and other technologies such as ion exchange technology, hydrophobic treatment technology, supercritical fluid extraction technology and bioleaching etc. The purpose of fly ash fusion solidification is to solidify most heavy metals in dense molten In the slag lattice structure, the possibility of heavy metal dissolution is greatly reduced, and the purpose of controlling heavy metal pollution is achieved. However, relying on chemical agents to control heavy metal pollution is costly and may cause secondary pollution. Therefore, finding an energy-efficient and environmentally friendly method is an urgent problem to be solved.
因此，针对目前我国垃圾燃烧飞灰重金属污染较为严重和冶金固废污染的双重难题，从“以废治污”的角度出发，发现冶金工业排放的固体废弃物“高炉瓦斯泥”，其成分较为复杂，含有约20％的氧化铁、23％的碳、较多的CaO、SiO2、Al2O3，以及其它少量、微量过渡金属的氧化物，可以在高温下与垃圾燃烧飞灰发生熔融，生成新的物相，从而降低垃圾飞灰中重金属的浸出率，达到排放标准。目前把这种冶金固废应用到治理垃圾飞灰重金属污染方面的研究还未见报到。因此，高炉瓦斯泥具备与垃圾燃烧飞灰混合后加热达到熔融固化重金属的基础。Therefore, in view of the serious heavy metal pollution of waste combustion fly ash and the pollution of metallurgical solid waste in China, from the perspective of "pollution control with waste", it is found that the solid waste "blast furnace gas mud" discharged from the metallurgical industry has a relatively high composition. Complex, containing about 20% iron oxide, 23% carbon, more CaO, SiO 2 , Al 2 O 3 , and other small and trace transition metal oxides, which can be fused with waste combustion fly ash at high temperature , to generate new phases, thereby reducing the leaching rate of heavy metals in garbage fly ash and meeting the emission standards. At present, there are no reports on the application of this metallurgical solid waste to the treatment of heavy metal pollution from garbage fly ash. Therefore, the blast furnace gas mud has the basis of mixing with waste combustion fly ash and heating to melt and solidify heavy metals.
发明内容Contents of the invention
为克服现有技术的不足，本发明要解决的技术问题是提供一种以高炉瓦斯泥和垃圾燃烧飞灰混合高温熔融固化重金属的方法，以期克服传统单纯依赖化学试剂和一次资源作为重金属络合剂的局限，为高炉瓦斯泥资源多组分高附加值利用提供新途径，也为控制垃圾飞灰重金属污染提供新的技术路线。In order to overcome the deficiencies in the prior art, the technical problem to be solved in the present invention is to provide a method of mixing high-temperature melting and solidifying heavy metals with blast furnace gas mud and waste combustion fly ash, in order to overcome the traditional dependence on chemical reagents and primary resources as heavy metal complexation It provides a new way for the multi-component high value-added utilization of blast furnace gas mud resources, and also provides a new technical route for controlling heavy metal pollution from waste fly ash.
为了解决以上技术问题，本发明是通过以下技术方案予以实现的。In order to solve the above technical problems, the present invention is achieved through the following technical solutions.
本发明提供了一种以高炉瓦斯泥和垃圾燃烧飞灰为原料混合高温熔融固化重金属的方法，该方法具体步骤如下：The invention provides a method for mixing high-temperature melting and solidifying heavy metals using blast furnace gas mud and waste combustion fly ash as raw materials. The specific steps of the method are as follows:
(1)将垃圾燃烧飞灰和高炉瓦斯泥按照9～1:1的比例混合均匀进行球磨，使样品中各成分充分接触；(1) Mix the waste combustion fly ash and blast furnace gas mud according to the ratio of 9 to 1:1 and perform ball milling to make the components in the sample fully contact;
(2)将步骤(1)制备的混合样品，分别放入管式炉中进行终温为800℃～1200℃的燃烧熔融固化，保温0.5到3小时。最后针对固化产物，按照国标进行As、Cd、Cr、Cu、Ni、Pd及Zn重金属浸出检测。(2) Put the mixed samples prepared in step (1) into a tube furnace for burning, melting and solidification at a final temperature of 800° C. to 1200° C., and keep the temperature for 0.5 to 3 hours. Finally, for the cured product, As, Cd, Cr, Cu, Ni, Pd and Zn heavy metal leaching tests were carried out according to the national standard.
作为一种优化，所述步骤(1)中：对高炉瓦斯泥和垃圾燃烧飞灰混合配比为1:1；所述步骤(2)中：考虑到能耗及混合样品中各组分的可发生熔融固化的最低温度问题，故此将混合样品加热熔融温度升高到1100℃，保温反应2h。As an optimization, in the step (1): the mixing ratio of blast furnace gas mud and waste combustion fly ash is 1:1; The lowest temperature problem of melting and solidification can occur, so the mixed sample is heated and melted to a temperature of 1100 ° C, and the reaction is kept for 2 hours.
本发明以高炉瓦斯泥和垃圾燃烧飞灰为原料混合高温熔融固化重金属的方法，其技术关键是作为垃圾燃烧飞灰重金属的固化剂，采用不同的添加比例，将混合产品加热到不同的温度熔融，最后得到固化产物，从而达到重金属固化的目的。该方法的特征是以瓦斯泥的多组分，含20％左右的氧化铁、23％左右的碳、较多的CaO、SiO2、Al2O3，以及其它少量、微量过渡金属，瓦斯泥中的主要成分与垃圾燃烧飞灰中的组分，在高温燃烧过程中，相互发生化学反应，重金属元素价态发生改变，与其他化学成分发生反应，生成新的固态物质，从而导致最后重金属浸出率降低，瓦斯泥中微量元素在燃烧固化过程中不产生明显负面影响。The method of the present invention uses blast furnace gas mud and waste combustion fly ash as raw materials to mix high-temperature melting and solidifying heavy metals. The technical key is to use different addition ratios to heat the mixed product to different temperatures and melt as a solidifying agent for heavy metals in waste combustion fly ash. , and finally get a cured product, so as to achieve the purpose of heavy metal solidification. The method is characterized by multi-component gas mud, containing about 20% iron oxide, about 23% carbon, more CaO, SiO 2 , Al 2 O 3 , and other small and trace transition metals, gas mud The main components in the fly ash and the components in the waste combustion fly ash, in the process of high temperature combustion, chemically react with each other, the valence state of heavy metal elements changes, and react with other chemical components to form new solid substances, resulting in the final leaching of heavy metals The rate is reduced, and the trace elements in the gas mud do not have obvious negative effects during the combustion and solidification process.
与现有技术相比，本发明具有以下技术效果：Compared with the prior art, the present invention has the following technical effects:
1、突破传统使用一次资源和纯化学试剂作为燃煤飞灰重金属络合剂的技术路线，而以冶金固体废弃物-高炉瓦斯泥为研究对象，利用瓦斯泥中主要组分Fe、Ca、Si以及Al等主要成分与垃圾燃烧飞灰的成分高温下发生熔融反应，生成新的固化产物达到重金属固化作用，起到代替重金属络合剂的作用，此方法突破了传统化学试剂或者一次资源络合垃圾飞灰重金属的局限，在降低控制重金属浸出成本的同时，也为冶金固废-高炉瓦斯尘泥无害化，资源化高附加值利用提供了新途径；1. Break through the traditional technical route of using primary resources and pure chemical reagents as heavy metal complexing agents for coal-fired fly ash, and take metallurgical solid waste-blast furnace gas mud as the research object, and use the main components of gas mud Fe, Ca, Si And the main components such as Al and the components of waste combustion fly ash undergo a melting reaction at high temperature to form a new solidified product to achieve the solidification of heavy metals and play the role of replacing heavy metal complexing agents. This method breaks through traditional chemical reagents or primary resource complexation The limitation of heavy metals in waste fly ash, while reducing the cost of controlling heavy metal leaching, also provides a new way for metallurgical solid waste-blast furnace gas dust and sludge to be harmless and resource-based with high added value;
2、与传统使用化学试剂合成或者一次资源络合垃圾燃烧飞灰重金属相比，本发明所述新方法利用高炉瓦斯泥混合垃圾燃烧飞灰高温熔融固化渣具有较好的控制重金属浸出效果，通过大量实验，重金属固化效果比较明显，完全达到了国家排放标准。2. Compared with the traditional synthesis of chemical reagents or the complexation of primary resources with heavy metals in the fly ash of waste combustion, the new method of the present invention uses blast furnace gas mud mixed with waste combustion fly ash to melt and solidify the slag at high temperature, which has a better effect of controlling the leaching of heavy metals. A large number of experiments have shown that the solidification effect of heavy metals is relatively obvious, which fully meets the national emission standards.
附图说明Description of drawings
图1为本发明实施例5制备的高炉瓦斯泥混合垃圾燃烧飞灰熔融固化重金属浸出图；Fig. 1 is the leaching figure of the heavy metal leaching of the blast furnace gas mud mixed waste combustion fly ash melting and solidification prepared in Example 5 of the present invention;
由图可见，随着尘泥添加剂加入垃圾燃烧飞灰的量比增加,各种重金属排放量明显下降。这说明高炉瓦斯泥加入到垃圾燃烧飞灰过程中，随着温度的升高，可有效的固化垃圾飞灰中的重金属，但是结合高炉瓦斯泥各种成分与垃圾燃烧飞灰中成分混合后发生的化学反应的机理，加入量过多会影响熔融反应的温度，考虑到能耗问题，故此将瓦斯泥与垃圾燃烧飞灰按照1:1的比例混合，重金属固化效果最佳，由此论证了高炉瓦斯泥在降低垃圾燃烧飞灰重金属浸出技术应用上的可行性。It can be seen from the figure that with the increase of the amount of dust additives added to waste combustion fly ash, the emissions of various heavy metals decreased significantly. This shows that when blast furnace gas mud is added to the process of waste combustion fly ash, as the temperature rises, it can effectively solidify the heavy metals in waste fly ash. The chemical reaction mechanism of the chemical reaction, too much addition will affect the temperature of the melting reaction, considering the energy consumption problem, so the gas mud and waste combustion fly ash are mixed according to the ratio of 1:1, and the solidification effect of heavy metals is the best, which demonstrates Feasibility of application of blast furnace gas mud in reducing heavy metal leaching from waste combustion fly ash.
具体实施方式detailed description
下面通过实施例具体详述本发明，但实施例并不限制本发明的保护范围。The present invention is described in detail below through examples, but the examples do not limit the protection scope of the present invention.
实施例1Example 1
取10g高炉瓦斯泥与90g垃圾燃烧飞灰进行研磨，达到充分混合，然后放入管式炉中，升温至800℃，保温0.5小时，最后针对固化产物，按照国标进行As、Cd、Cr、Cu、Ni、Pd及Zn重金属浸出检测。Take 10g of blast furnace gas mud and 90g of waste combustion fly ash for grinding to achieve thorough mixing, then put it into a tube furnace, raise the temperature to 800°C, and keep it warm for 0.5 hours. Finally, for the solidified product, As, Cd, Cr, Cu , Ni, Pd and Zn heavy metal leaching detection.
实施例2Example 2
取20g高炉瓦斯泥与80g垃圾燃烧飞灰进行研磨，达到充分混合，然后放入管式炉中，升温至900℃，保温1小时，最后针对固化产物，按照国标进行As、Cd、Cr、Cu、Ni、Pd及Zn重金属浸出检测。Take 20g of blast furnace gas mud and 80g of waste combustion fly ash and grind them to achieve thorough mixing, then put them into a tube furnace, raise the temperature to 900°C, and keep it warm for 1 hour. , Ni, Pd and Zn heavy metal leaching detection.
实施例3Example 3
取30g高炉瓦斯泥与70g垃圾燃烧飞灰进行研磨，达到充分混合，然后放入管式炉中，升温至1000℃，保温1.5小时，最后针对固化产物，按照国标进行As、Cd、Cr、Cu、Ni、Pd及Zn重金属浸出检测。Take 30g of blast furnace gas mud and 70g of waste combustion fly ash for grinding to achieve full mixing, then put it into a tube furnace, raise the temperature to 1000°C, keep it warm for 1.5 hours, and finally carry out As, Cd, Cr, Cu for the solidified product according to national standards , Ni, Pd and Zn heavy metal leaching detection.
实施例4Example 4
取40g高炉瓦斯泥与60g垃圾燃烧飞灰进行研磨，达到充分混合，然后放入管式炉中，升温至1200℃，保温3小时，最后针对固化产物，按照国标进行As、Cd、Cr、Cu、Ni、Pd及Zn重金属浸出检测。Take 40g of blast furnace gas mud and 60g of waste combustion fly ash and grind them to achieve thorough mixing, then put them into a tube furnace, raise the temperature to 1200°C, and keep them warm for 3 hours. , Ni, Pd and Zn heavy metal leaching detection.
实施例5Example 5
取50高炉瓦斯泥与50g垃圾燃烧飞灰进行研磨，达到充分混合，然后放入管式炉中，升温至1100℃，保温2小时，最后针对固化产物，按照国标进行As、Cd、Cr、Cu、Ni、Pd及Zn重金属浸出检测。Grind 50g of blast furnace gas mud and 50g of waste combustion fly ash to achieve thorough mixing, then put it into a tube furnace, raise the temperature to 1100°C, and keep it warm for 2 hours. Finally, for the solidified product, As, Cd, Cr, Cu , Ni, Pd and Zn heavy metal leaching detection.
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