CN107473710A - A kind of electroplating sludge that blends prepares the method that clay brick process improves heavy metals immobilization effect - Google Patents
A kind of electroplating sludge that blends prepares the method that clay brick process improves heavy metals immobilization effect Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 74
- 238000009713 electroplating Methods 0.000 title claims abstract description 69
- 239000011449 brick Substances 0.000 title claims abstract description 63
- 239000004927 clay Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 34
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000011521 glass Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000007711 solidification Methods 0.000 claims abstract description 16
- 230000008023 solidification Effects 0.000 claims abstract description 16
- 239000002699 waste material Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims description 25
- 238000002386 leaching Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 235000012054 meals Nutrition 0.000 claims description 13
- 239000002910 solid waste Substances 0.000 claims description 9
- 230000006835 compression Effects 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 231100000331 toxic Toxicity 0.000 claims description 6
- 230000002588 toxic effect Effects 0.000 claims description 6
- 239000006063 cullet Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 238000005554 pickling Methods 0.000 claims 2
- 239000010959 steel Substances 0.000 claims 2
- 238000009837 dry grinding Methods 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000011800 void material Substances 0.000 abstract description 5
- 239000005337 ground glass Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000004568 cement Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
- C04B35/62615—High energy or reactive ball milling
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Sludge (AREA)
Abstract
本发明公开了一种在掺混电镀污泥制备粘土砖过程中提高重金属固化效果的方法。在掺混电镀污泥制备粘土砖过程中加入废玻璃粉，玻璃粉在高温时首先软化和熔融形成液相，液相填充在砖体内部的空隙结构中，达到降低砖体孔隙率和比表面积的目的，从而提高重金属的固化效果。本发明的具体工艺步骤为：(1)将磨细的玻璃粉与电镀污泥和粘土混合物粉磨混合，玻璃粉的加入量为质量分数10‑35％，经制砖机压制成型后得到砖坯；(2)将干燥的砖坯在900‑1200℃煅烧3‑5h。本发明具有原料来源广、经济性好，提升固化效果明显等优点。The invention discloses a method for improving the solidification effect of heavy metals in the process of mixing electroplating sludge to prepare clay bricks. Waste glass powder is added in the process of mixing electroplating sludge to prepare clay bricks. The glass powder first softens and melts to form a liquid phase at high temperature, and the liquid phase fills the void structure inside the brick body to reduce the porosity and specific surface area of the brick body. The purpose, thereby improving the curing effect of heavy metals. The specific process steps of the present invention are: (1) Grinding and mixing the finely ground glass powder with the electroplating sludge and clay mixture, the glass powder is added in an amount of 10-35% by mass, and the adobe is obtained after being pressed and formed by a brick making machine ; (2) calcining the dried adobe at 900-1200°C for 3-5h. The invention has the advantages of wide source of raw materials, good economy, obvious enhancement of curing effect and the like.
Description
技术领域technical field
本发明涉及固体废弃物资源化利用领域，具体是涉及一种在掺混电镀污泥制备粘土砖过程中采用废玻璃粉以提高重金属固化效果的方法。The invention relates to the field of resource utilization of solid waste, in particular to a method for improving the solidification effect of heavy metals by using waste glass powder in the process of mixing electroplating sludge to prepare clay bricks.
背景技术Background technique
电镀污泥是电镀生产过程中产生的电镀废水和废旧电镀液在处理过程中产生的固体废弃物，由于含有大量的重金属，且重金属的存在形态基本为水合物，极易被浸出到环境中，因而电镀污泥一直以来都被认为是典型的危险废物。由于重金属不能被物理或者化学分解，所以电镀污泥的处理只能采用回收和固化/稳定化的方法。电镀污泥中重金属的回收一般采用酸浸后经化学沉淀、离子交换、膜分离、萃取等方法实现从液相中分离回收重金属离子的目的。虽然这些回收的方法分离回收的效率较高，但是受限于技术及经济性的原因，电镀污泥的回收利用并不广泛。Electroplating sludge is the solid waste generated during the treatment of electroplating wastewater and waste electroplating solutions in the electroplating production process. Because it contains a large amount of heavy metals, and the existence of heavy metals is basically hydrate, it is very easy to be leached into the environment. Therefore, electroplating sludge has always been considered as a typical hazardous waste. Since heavy metals cannot be physically or chemically decomposed, the treatment of electroplating sludge can only be done by recycling and solidification/stabilization. The recovery of heavy metals in electroplating sludge generally adopts acid leaching followed by chemical precipitation, ion exchange, membrane separation, extraction and other methods to achieve the purpose of separating and recovering heavy metal ions from the liquid phase. Although the separation and recovery efficiency of these recycling methods is high, the recycling of electroplating sludge is not widely used due to technical and economical reasons.
目前固化/稳定化仍然是电镀污泥处理的最主要的方法，主要包括水泥、玻璃等包覆固化。申请号CN201510207253.0公开了一种电镀污泥的稳定化方法，先将待处理的电镀污泥与飞灰混合，持续搅拌作用下分别加入氢氧化钙粉末、水泥和水，搅拌均匀，得到浆状混合物；将浆状混合物倒入模具中并进行养护；待固化体表面干燥后，将环氧树脂及对应的固化剂混合，均匀涂覆在固化体表面；树脂涂覆层固化完全后得到可以直接填埋的电镀污泥固化体。申请号CN201510874164.1公开了一种电镀污泥的固化方法，固化剂采用水泥等，具体包括以下重量百分数的原料制备而成：水泥75％～79％、砂10％～15％、硅酸钠5％～8％、活性氧化铝6％～10％。At present, solidification/stabilization is still the most important method for electroplating sludge treatment, mainly including coating and solidification of cement and glass. Application number CN201510207253.0 discloses a stabilization method for electroplating sludge. Firstly, the electroplating sludge to be treated is mixed with fly ash, and calcium hydroxide powder, cement and water are respectively added under continuous stirring, and stirred evenly to obtain slurry Pour the slurry mixture into the mold and perform maintenance; after the surface of the cured body is dry, mix the epoxy resin and the corresponding curing agent, and evenly coat the surface of the cured body; after the resin coating layer is cured completely, it can be Solidification of electroplating sludge directly landfilled. Application number CN201510874164.1 discloses a solidification method of electroplating sludge. The solidification agent is prepared from cement, etc., specifically including the following raw materials in weight percentage: cement 75%-79%, sand 10%-15%, sodium silicate 5% to 8%, activated alumina 6% to 10%.
除了采用包覆固化外，掺混电镀污泥高温烧制粘土砖也是一种有效的固化电镀污泥的方法，且制备的粘土砖具有进一步资源化利用的潜能。掺混电镀污泥在高温烧制粘土砖过程中，重金属会与粘土中的SiO2、Al2O3、Fe2O3反应形成一些稳定的矿物相结构，从而抑制重金属的浸出；另外粘土砖在烧制过程中会形成致密的砖体结构也可以起到包覆重金属减少其浸出风险的作用。虽然掺混电镀污泥高温烧制粘土砖可以起到显著减少重金属浸出的作用，但是当电镀污泥的掺混量提高或者粘土砖的孔隙结构过于发达时，会由于有较多的重金属物相与浸出液接触，导致仍然有很多的重金属被浸出。因此如何在掺混电镀污泥高温烧制粘土砖过程中减少粘土砖的孔隙结构，减少重金属与浸出液的接触面积将是提高重金属固化效果的关键。提高粘土砖压制过程的压强是一种手段，但是粘土和电镀污泥中的有机物在高温下仍然后分解燃烧形成气体，气体从砖体内部往外逸散的过程仍然会在砖体内部形成空隙结构。In addition to encapsulation and curing, high-temperature firing clay bricks mixed with electroplating sludge is also an effective method for curing electroplating sludge, and the prepared clay bricks have the potential for further resource utilization. In the process of firing clay bricks with mixed electroplating sludge at high temperature, heavy metals will react with SiO 2 , Al 2 O 3 , and Fe 2 O 3 in the clay to form some stable mineral phase structures, thereby inhibiting the leaching of heavy metals; The dense brick structure formed during the firing process can also play a role in covering heavy metals to reduce the risk of their leaching. Although mixing electroplating sludge and firing clay bricks at high temperature can significantly reduce the leaching of heavy metals, when the mixing amount of electroplating sludge is increased or the pore structure of clay bricks is too developed, there will be more heavy metal phases. In contact with the leach solution, a lot of heavy metals are still leached. Therefore, how to reduce the pore structure of clay bricks and reduce the contact area between heavy metals and leachate during the high-temperature firing of clay bricks with electroplating sludge will be the key to improving the solidification effect of heavy metals. Improving the pressure of the clay brick pressing process is a means, but the organic matter in the clay and electroplating sludge still decomposes and burns to form gas at high temperature, and the process of gas escaping from the inside of the brick body will still form a void structure inside the brick body .
碎玻璃是生活中常见的无机固体废弃物，玻璃的熔点及软化温度要低于粘土，因此在粘土砖中掺入碎玻璃粉，其在高温条件下软化熔融从而能够起到粘结、填充孔径的作用，从而可以有效降低砖体的空隙结构，达到降低重金属溶出的目的。Broken glass is a common inorganic solid waste in daily life. The melting point and softening temperature of glass are lower than that of clay. Therefore, cullet powder is mixed into clay bricks, which can be softened and melted under high temperature conditions to bond and fill pores. Therefore, it can effectively reduce the void structure of the brick body and achieve the purpose of reducing the dissolution of heavy metals.
本发明意在掺混电镀污泥制备粘土砖过程中加入碎玻璃粉，利用玻璃熔点低的特点，填充、堵塞砖体内部的空隙结构，从而达到大幅降低砖体内部空隙和提高重金属固化的效果。The present invention intends to add crushed glass powder in the process of mixing electroplating sludge to prepare clay bricks, and utilizes the characteristics of low melting point of glass to fill and block the void structure inside the brick body, so as to greatly reduce the internal voids of the brick body and improve the solidification effect of heavy metals .
发明内容Contents of the invention
本发明所要解决的问题是掺混电镀污泥高温制备粘土砖电镀污泥产量少、固化效果不佳的问题，以碎玻璃粉作为砖体空隙填充剂，通过在粘土砖制备过程加入碎玻璃粉的方法达到减少砖体内部的孔隙和提高电镀污泥的固化效果。具体是一种利用碎玻璃粉提高掺混电镀污泥制备粘土砖过程重金属固化效果的方法。The problem to be solved by the present invention is the low output of electroplating sludge and poor curing effect when mixing electroplating sludge at high temperature to prepare clay bricks. The broken glass powder is used as the brick body gap filler, and the broken glass powder is added in the clay brick preparation process. The method can reduce the pores inside the brick body and improve the curing effect of electroplating sludge. Specifically, it is a method for improving the solidification effect of heavy metals in the process of preparing clay bricks by mixing electroplating sludge by using broken glass powder.
一种掺混电镀污泥制备粘土砖过程提高重金属固化效果的方法，包括以下步骤：A method for improving the solidification effect of heavy metals in the process of mixing electroplating sludge to prepare clay bricks, comprising the following steps:
1.将碎玻璃经过球磨机干磨成粉，球磨时间为2-6h，将得到的废玻璃粉通过200目的筛子以获得相同粒径大小的废玻璃粉。1. The cullet is dry-milled into powder through a ball mill, and the ball milling time is 2-6 hours. Pass the obtained waste glass powder through a 200-mesh sieve to obtain waste glass powder with the same particle size.
2.将采集的电镀污泥和粘土在105℃烘干24h，随后将烘干的电镀污泥和粘土经球磨机中粉碎、磨细，球磨机转速50-100r/min，球磨时间0.5-2h，含铁污泥和粘土也要通过200目的筛子以获得相同粒径大小的原料。2. Dry the collected electroplating sludge and clay at 105°C for 24 hours, then pulverize and finely grind the dried electroplating sludge and clay in a ball mill, the speed of the ball mill is 50-100r/min, and the ball milling time is 0.5-2h Iron sludge and clay are also passed through a 200-mesh sieve to obtain raw materials of the same particle size.
3.将烘干磨细的电镀污泥和粘土混合，电镀污泥和粘土的质量分数分别为10％和90％，将混合的生料经球磨机混合，球磨时间2-4h。3. Mix the dried and finely ground electroplating sludge and clay, the mass fractions of the electroplating sludge and clay are 10% and 90% respectively, and mix the mixed raw materials through a ball mill, and the ball milling time is 2-4h.
4.向上述混合好的电镀污泥和粘土混合生料加入磨细的废玻璃粉，玻璃粉的加入量为质量分数10-35％，所得的混合生料再次经球磨混合，球磨混合时间为2-4h。4. Add finely ground waste glass powder to the above-mentioned mixed electroplating sludge and clay mixed raw meal, the addition of glass powder is a mass fraction of 10-35%, and the mixed raw meal of gained is mixed again through ball milling, and the ball milling mixing time is 2-4h.
5.将所得混合生料经制砖机压缩，压缩压强为40-60MPa，圧缩前可往生料中加入少量水以提高其压缩可塑性，水的加入量为生料的5-10％(质量分数)。5. Compress the mixed raw meal by the brick making machine, the compression pressure is 40-60MPa, a small amount of water can be added to the raw meal before compression to improve its compression plasticity, the amount of water added is 5-10% of the raw meal (mass Fraction).
6.经制砖机制成砖坯在110℃烘干24h，所得砖坯在高温900-1200℃煅烧3-5h，高温煅烧结束后，停止加热，自然冷却至室温。6. The adobe made by the brick making machine is dried at 110°C for 24 hours, and the obtained adobe is calcined at a high temperature of 900-1200°C for 3-5 hours. After the high-temperature calcination, stop heating and cool naturally to room temperature.
7.将煅烧过的砖块采用国家标准《固体废物毒性浸出方法-醋酸缓冲溶液法》(HJ/T300-2007)方法对煅烧后的粉末浸出，浸出结束后取样检测浸出液中的重金属浓度。7. The calcined bricks are leached from the calcined powder using the national standard "Solid Waste Toxic Leaching Method-Acetic Acid Buffer Solution Method" (HJ/T300-2007), and after the leaching is completed, samples are taken to detect the concentration of heavy metals in the leachate.
本发明的提高电镀污泥固化效果的原理是：(1)废玻璃粉的熔融填充砖体内部空隙结构。熔融的温度较粘土要低，意味着玻璃粉在较低的温度下就能熔融形成液相；在粘土结构形成框架支撑结构，废玻璃熔融形成的液相可以填充在砖块内部的空隙中，因而可以显著降低砖块的内部孔容和比表面积，减少后期浸出过程中砖块与浸出液的接触面积，达到降低重金属浸出的目的。(2)废玻璃粉熔融过程形成液相，会吞并和粘结玻璃粉周围的电镀污泥，并将其纳入玻璃结构中，达到玻璃固化的效果。上述两种原理即为玻璃粉提高固化效果的机理。The principle of improving the solidification effect of the electroplating sludge of the present invention is: (1) the melting of waste glass powder fills the internal void structure of the brick body. The melting temperature is lower than that of clay, which means that glass powder can be melted to form a liquid phase at a lower temperature; the clay structure forms a frame support structure, and the liquid phase formed by the melting of waste glass can fill the voids inside the brick. Therefore, the internal pore volume and specific surface area of the brick can be significantly reduced, and the contact area between the brick and the leachate in the later leaching process can be reduced, so as to achieve the purpose of reducing the leaching of heavy metals. (2) The liquid phase is formed during the melting process of waste glass powder, which will swallow up and bond the electroplating sludge around the glass powder, and incorporate it into the glass structure to achieve the effect of vitrification. The above two principles are the mechanism for glass powder to improve the curing effect.
本发明具有原料来源广泛、成本低、经济性能好，可资源化利用的优点。The invention has the advantages of wide source of raw materials, low cost, good economic performance and resourceful utilization.
具体实施方式detailed description
下面结合实例，对本发明作进一步描述，以下实施例旨在说明本发明而不是对本发明的进一步限定。The present invention will be further described below in conjunction with examples, and the following examples are intended to illustrate the present invention rather than further limit the present invention.
示例1Example 1
将采集的电镀污泥和粘土在105℃烘干24h，随后将烘干的含铁污泥和电镀污泥分别至于球磨机中粉碎、磨细，球磨机转速50r/min，球磨时间0.5h。将烘干磨细的电镀污泥和粘土混合，电镀污泥和粘土的质量分数分别为10％和90％，将混合的生料经球磨机混合，球磨时间4h。将所得混合生料经制砖机压制成砖后于105℃烘干24h，烘干后的砖坯在1000℃煅烧4h，自然冷却后室温后取出。将所制备的粘土砖经《固体废物毒性浸出方法-醋酸缓冲溶液法》(HJ/T300-2007)浸出18h，浸出结束后溶液中的重金属Cr、Cu、Zn、Ni的浓度分别为20、75、65、8mg/L，未能达到国家危险废物鉴别技术规范(HJ/T298-2007)的要求(HJ/T298-2007要求Cr、Cu、Zn、Ni的浓度分别为15、100、100、5mg/L)。The collected electroplating sludge and clay were dried at 105°C for 24 hours, and then the dried iron-containing sludge and electroplating sludge were pulverized and finely ground in a ball mill with a ball mill speed of 50r/min and a ball milling time of 0.5h. The dried and ground electroplating sludge and clay are mixed, the mass fractions of the electroplating sludge and clay are 10% and 90% respectively, and the mixed raw meal is mixed by a ball mill, and the ball milling time is 4h. The obtained mixed raw materials are pressed into bricks by a brick making machine and dried at 105°C for 24 hours. The dried bricks are calcined at 1000°C for 4 hours, cooled naturally and taken out at room temperature. The prepared clay bricks were leached for 18 hours through "Solid Waste Toxic Leaching Method-Acetic Acid Buffer Solution Method" (HJ/T300-2007). . /L).
将采集的玻璃粉经球磨机粉磨4h，过200目筛子。The collected glass powder was ground by a ball mill for 4 hours, and passed through a 200-mesh sieve.
示例2Example 2
将采集的电镀污泥和粘土在105℃烘干24h，随后将烘干的含铁污泥和电镀污泥分别至于球磨机中粉碎、磨细，球磨机转速50r/min，球磨时间0.5h。将烘干磨细的电镀污泥和粘土混合，电镀污泥和粘土的质量分数分别为10％和90％，将混合的生料经球磨机混合，球磨时间4h。将采集的玻璃粉经球磨机粉磨4h，过200目筛子；将磨细的玻璃粉与电镀污泥和粘土混合生料混合，球磨混合时间为4h，废玻璃粉加入量为质量分数10％；将所得混合生料经制砖机压制成砖后于105℃烘干24h，烘干后的砖坯在1000℃煅烧4h，自然冷却后室温后取出。将所制备的粘土砖经《固体废物毒性浸出方法-醋酸缓冲溶液法》(HJ/T300-2007)浸出18h，浸出结束后溶液中的重金属Cr、Cu、Zn、Ni的浓度分别为10、43、38、3.6mg/L，达到了国家危险废物鉴别技术规范(HJ/T298-2007)的要求(HJ/T298-2007要求Cr、Cu、Zn、Ni的浓度分别为15、100、100、5mg/L)，说明玻璃粉的加入能明显降低粘土砖中重金属的浸出，提高重金属的固化效果。The collected electroplating sludge and clay were dried at 105°C for 24 hours, and then the dried iron-containing sludge and electroplating sludge were pulverized and finely ground in a ball mill with a ball mill speed of 50r/min and a ball milling time of 0.5h. The dried and ground electroplating sludge and clay are mixed, the mass fractions of the electroplating sludge and clay are 10% and 90% respectively, and the mixed raw meal is mixed by a ball mill, and the ball milling time is 4h. Grind the collected glass powder with a ball mill for 4 hours and pass through a 200-mesh sieve; mix the finely ground glass powder with electroplating sludge and clay mixed raw materials, the mixing time of ball milling is 4 hours, and the amount of waste glass powder added is 10% by mass fraction; The obtained mixed raw materials are pressed into bricks by a brick making machine and dried at 105°C for 24 hours. The dried bricks are calcined at 1000°C for 4 hours, cooled naturally and taken out at room temperature. The prepared clay bricks were leached for 18 hours through "Solid Waste Toxic Leaching Method-Acetic Acid Buffer Solution Method" (HJ/T300-2007). . /L), indicating that the addition of glass powder can significantly reduce the leaching of heavy metals in clay bricks and improve the curing effect of heavy metals.
示例3Example 3
将采集的电镀污泥和粘土在105℃烘干24h，随后将烘干的含铁污泥和电镀污泥分别至于球磨机中粉碎、磨细，球磨机转速50r/min，球磨时间0.5h。将烘干磨细的电镀污泥和粘土混合，电镀污泥和粘土的质量分数分别为10％和90％，将混合的生料经球磨机混合，球磨时间4h。将采集的玻璃粉经球磨机粉磨4h，过200目筛子；将磨细的玻璃粉与电镀污泥和粘土混合生料混合，球磨混合时间为4h，废玻璃粉加入量为质量分数20％；将所得混合生料经制砖机压制成砖后于105℃烘干24h，烘干后的砖坯在1100℃煅烧4h，自然冷却后室温后取出。将所制备的粘土砖经《固体废物毒性浸出方法-醋酸缓冲溶液法》(HJ/T300-2007)浸出18h，浸出结束后溶液中的重金属Cr、Cu、Zn、Ni的浓度分别为8、33、29、2.5mg/L，达到了国家危险废物鉴别技术规范(HJ/T298-2007)的要求(HJ/T298-2007要求Cr、Cu、Zn、Ni的浓度分别为15、100、100、5mg/L)，说明玻璃粉的加入能明显降低粘土砖中重金属的浸出，提高重金属的固化效果。The collected electroplating sludge and clay were dried at 105°C for 24 hours, and then the dried iron-containing sludge and electroplating sludge were pulverized and finely ground in a ball mill with a ball mill speed of 50r/min and a ball milling time of 0.5h. The dried and ground electroplating sludge and clay are mixed, the mass fractions of the electroplating sludge and clay are 10% and 90% respectively, and the mixed raw meal is mixed by a ball mill, and the ball milling time is 4h. Grind the collected glass powder with a ball mill for 4 hours, and pass through a 200-mesh sieve; mix the ground glass powder with electroplating sludge and clay mixed raw material, the mixing time of ball milling is 4 hours, and the amount of waste glass powder added is 20% by mass fraction; The obtained mixed raw materials are pressed into bricks by a brick making machine and dried at 105°C for 24 hours. The dried bricks are calcined at 1100°C for 4 hours, cooled naturally and taken out at room temperature. The prepared clay bricks were leached for 18 hours through "Solid Waste Toxic Leaching Method-Acetic Acid Buffer Solution Method" (HJ/T300-2007). After the leaching, the concentrations of heavy metals Cr, Cu, Zn, and Ni in the solution were 8, 33 . /L), indicating that the addition of glass powder can significantly reduce the leaching of heavy metals in clay bricks and improve the curing effect of heavy metals.
示例4Example 4
将采集的电镀污泥和粘土在105℃烘干24h，随后将烘干的含铁污泥和电镀污泥分别至于球磨机中粉碎、磨细，球磨机转速50r/min，球磨时间0.5h。将烘干磨细的电镀污泥和粘土混合，电镀污泥和粘土的质量分数分别为10％和90％，将混合的生料经球磨机混合，球磨时间4h。将采集的玻璃粉经球磨机粉磨4h，过200目筛子；将磨细的玻璃粉与电镀污泥和粘土混合生料混合，球磨混合时间为4h，废玻璃粉加入量为质量分数35％；将所得混合生料经制砖机压制成砖后于105℃烘干24h，烘干后的砖坯在1200℃煅烧4h，自然冷却后室温后取出。将所制备的粘土砖经《固体废物毒性浸出方法-醋酸缓冲溶液法》(HJ/T300-2007)浸出18h，浸出结束后溶液中的重金属Cr、Cu、Zn、Ni的浓度分别为2.1、14、10、0.7mg/L，达到了国家危险废物鉴别技术规范(HJ/T298-2007)的要求(HJ/T298-2007要求Cr、Cu、Zn、Ni的浓度分别为15、100、100、5mg/L)，说明玻璃粉的加入能明显降低粘土砖中重金属的浸出，提高重金属的固化效果。The collected electroplating sludge and clay were dried at 105°C for 24 hours, and then the dried iron-containing sludge and electroplating sludge were pulverized and finely ground in a ball mill with a ball mill speed of 50r/min and a ball milling time of 0.5h. The dried and ground electroplating sludge and clay are mixed, the mass fractions of the electroplating sludge and clay are 10% and 90% respectively, and the mixed raw meal is mixed by a ball mill, and the ball milling time is 4h. Grind the collected glass powder with a ball mill for 4 hours, and pass through a 200-mesh sieve; mix the ground glass powder with electroplating sludge and clay mixed raw material, the mixing time of ball milling is 4 hours, and the amount of waste glass powder added is 35% by mass fraction; The obtained mixed raw materials are pressed into bricks by a brick making machine and dried at 105°C for 24 hours. The dried bricks are calcined at 1200°C for 4 hours, cooled naturally and taken out at room temperature. The prepared clay bricks were leached for 18 hours through "Solid Waste Toxic Leaching Method-Acetic Acid Buffer Solution Method" (HJ/T300-2007). . /L), indicating that the addition of glass powder can significantly reduce the leaching of heavy metals in clay bricks and improve the curing effect of heavy metals.
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| CN110357576A (en) * | 2019-08-12 | 2019-10-22 | 常州大学 | Blend the method that waterglass promotes the performance and heavy metals immobilization effect of clay brick |
| CN112159205A (en) * | 2020-09-10 | 2021-01-01 | 广东工业大学 | Iron tailing baked brick and preparation method thereof |
| CN113149607A (en) * | 2021-04-14 | 2021-07-23 | 天津城建大学 | Sludge brick heavy metal curing agent, sludge brick and preparation method of sludge brick |
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