Study on preparation of glass-ceramics from multiple solid waste and coupling mechanism of heavy metals

Solid wastes, such as municipal solid waste incineration fly ash (MSWI FA) and tailings, contain a large number of harmful components, which makes harmless and recycling treatment a challenge. Through high-temperature reconstruction, the solid waste containing heavy metals is prepared into glass-ceramics, which is an effective method to realize the harmless and resource utilization of solid waste. In this work, glass-ceramics were successfully prepared by using MSWI FA, waste glass, and lead-zinc tailings. The utilization rate of solid waste reached 91.74%. The coupling mechanism of heavy metals with Fe as the dominant factor and Zn, Cu, and Pb coexisting was explored. The results showed that the critical threshold of sintering temperature was 1000 °C. The properties of glass-ceramics can be greatly optimized when the temperature was higher than 1000 °C. Fe played a leading role in the migration and solidification process. Because of its higher displacement capacity, Fe was preferentially solidified in the form of hedenbergite and magnetite. Zn, Cu, and Pb solidified in the form of (Mg,Fe,Zn,Cu)Fe₂O₄ and Pb²⁺ respectively. The order of stabilization effect was Fe > Zn > Cu > Pb. All leaching concentrations of heavy metals were lower than the standard threshold, even if the heavy metals reached 20 wt%.     

Migration,transformation and solidification/stabilization mechanisms of heavy metals in glass-ceramics made from MSWI fly ash and pickling sludge

In consideration of recycling solid waste to achieve high value-added products, glass-ceramics have been fabricated from municipal solid waste incineration (MSWI) fly ash, pickling sludge (PS), and waste glass (WG) by melting at 1450 °C firstly to achieve parent glass and then crystallizing at 850 °C. Results demonstrated that heavy metals have been well solidified in the prepared glass-ceramics, and relatively/extremely low leaching concentrations of heavy metals have been detected. The synthetic toxicity index of heavy metals has been greatly reduced from 7-18 to <3.2 after crystallization treatment, and the leaching concentrations of Cr, Ni, Zn, Cu, and Pb are 0.15, 0.05, 0.26, 0.12, 0.19 mg L^-1 respectively. Chemical morphology analysis, principal component analysis, TEM and EPMA were utilized to clarify the migration, transformation, and solidification mechanism of heavy metals from the as-received solid wastes. The major heavy metals, Cr and Ni which is responsible for the most toxicity, mainly exist in form of the oxidation state and residual state in parent glass, while the residual state in the glass-ceramics. The solidification performance was mostly positively correlated with the form of residue state, which the stability of heavy metals in glass-ceramics is improved. The solidification mechanism of heavy metals in glass-ceramics could be explained by the combination of chemical solidification/stabilization and physical coating. The TEM and EPMA confirmed that Cr and Ni mainly exist in the spinel crystalline (NiCr₂O₄, Fe_0.99Ni_0.01Fe_1.97Cr_0.03O₄) by solid solution or chemical substitution, and a small amount of Cr in the diopside phase. Pb, Cu, and Zn are homogenously dispersed in the glass-ceramics, which is considered as physical coating solidification.     

Potential utilization of oil sludge incineration bottom ash for glass-ceramics: Crystallization kinetics,properties and toxicological evaluation

The bottom ash (OIBA) generated from the incineration of hazardous oil sludge is classified as a hazardous waste. In this work, the OIBA was applied as raw material to prepare SiO₂-Al₂O₃-CaO system glass-ceramics by melt-sintering with the addition of waste glass wool (GW). The effects of basicity (CaO/SiO₂ ratio, 0.52-1.05) and sintering temperature (900–1050 °C) on the crystallization kinetics, properties, microstructure, leaching concentrations of heavy metals and potential toxicity of glass-ceramics were investigated. The results showed that the crystallization pattern was two-dimensional crystallization, and with the decrease of basicity, the main crystalline phase evolved from gehlenite to diopside. And the glass-ceramics with basicity of 0.88 and sintering temperature of 950 °C exhibited the best comprehensive properties, including density (2.72 g/cm³), water absorption (0.06%), compressive strength (452.45 MPa) and chemical corrosion resistance. In addition, the reduction of heavy metal leaching concentration indicates that produced glass-ceramics showed excellent solidification effect on heavy metals, the low toxicity of glass-ceramics leaching solution to the wheat seeds and Artemia suggests the environmental protection characteristics of OIBA-based glass-ceramics. These findings proved that the glass-ceramics produced by OIBA and GW could be a promising method to dispose hazardous waste with preparing high value-added construction materials.     

Stabilization of electric arc furnace dust by the use of cementitious materials: Ionic competition and long-term leachability

Ionic competition in stabilization of major heavy metals from electric arc furnace dust (EAFD) was investigated. The cementitious materials tested (ground granulated blast furnace slag (GGBFS) and ordinary Portland cement (OPC)) were put in contact with solutions made of various combinations of Cr(VI), Pb(II), Zn(II), Ni(II) and Mo(VI) ions. The presence of Ni, Zn or Mo did not influence the Cr fixation by GGBFS and OPC. The ionic competition phenomenon between Cr and Pb was observed for GGBFS in particular.Long-term leaching tests with OPC-EAFD and GGBFS-EAFD showed that OPC is more effective in fixing Cr at 7 days (4.7 mg/L in solution) than GGBFS (79.4 mg/L in solution). GGBFS becomes effective with time and offers a better performance from 56 to 365 days (under 1 mg/L in solution) than OPC (until 11 mg/L in solution). GGBFS and OPC decreased Zn, Pb and Ni concentrations in leaching solutions under 2.5 mg/L.     

Content, mobility and transfer behavior of heavy metals in MSWI bottom ash in Zhejiang province, China

Municipal solid waste incinerator (MSWI) bottom ash samples were taken from six cities of Zhejiang province, where 1/4 incinerators of China were located. The samples were instrumentally analyzed to detect the content of heavy metals. Sequential extraction procedure (SEP) was adopted to characterize the mobility and environmental impact of heavy metals. And the transfer coefficients of heavy metals from the input MSW to the bottom ash during the incineration were also calculated. It showed that the average content of Zn, Mn, Cu, Pb and Cr in the bottom ash exceeded 300 mg/kg, which was much higher than that in the soils. SEP results showed that although the residue fraction was the primary fraction of the heavy metals in the bottom ash, there were still 1.84 mg of Cd, 86.21 mg of Cu, 83.46 mg of Pb and 939.46 mg of Zn in 1 kg bottom ash having the potential of leaching, which indicated a great threat to the surrounding environment. The result of coefficients calculation revealed that almost all the Cu, Cr, Mn and Ni in the input MSW were transferred to the bottom ash during the incineration. Bottom ash was also the main destination of Cd, Co, As, Mo, Pb and Zn though considerable amounts of those metals were transferred to the raw gas.     

Preparation and characterization of fully waste-based glass-ceramics from incineration fly ash,waste glass and coal fly ash

Municipal solid waste incineration (MSWI) fly ash (FA) is a typical hazardous waste due to its high contents of toxic heavy metals, and hence its disposal has attracted global concern. In this work, it was recycled into environmental-friendly CaO–Al₂O₃–SiO₂ system glass-ceramics via adding coal fly ash (CFA) and waste glass (WG). The effects of CaO/SiO₂ ratios and sintering temperatures on the crystalline phases, morphologies, mechanical and chemical properties, heavy metals leaching and potential ecological risks of glass-ceramics were investigated. The results showed that wollastonite (CaSiO₃), anorthite (CaAl₂Si₂O₈) and gehlenite (Ca₂Al₂SiO₇) were the dominant crystals in the glass-ceramics, which were not affected by CaO/SiO₂ ratio and sintering temperature. The compressive strength increased, while the Vickers hardness and microhardness decreased as increasing the sintering temperatures from 850 to 1050 °C, which reached their maximum values of 660.69 MPa, 6.14 GPa, and 7.43 GPa, respectively. However, the increase of CaO/SiO₂ ratio resulted into the reduction of the three mechanical parameters. As varying CaO/SiO₂ ratio from 0.48 to 0.86, the maximum compressive strength, Vickers hardness and microhardness were 611.80 MPa, 5.43 GPa, and 6.56 GPa, respectively. Besides, all the glass-ceramics exhibited high alkali resistance of >97%. The extremely low heavy metals leaching concentrations and low potential ecological risk of glass-ceramics further revealed its environmentally friendly property and potential application feasibility.     

The direct experimental observation and solidification mechanism of heavy metals in blast furnace slag glass-ceramics

Glass-ceramics with high performance and high crystallinity was produced using rare earth blast furnace slag (REBFS) as the primary raw material, along with composite nucleating agents Fe₂O₃ and Cr₂O₃. The migration pattern, distribution characteristics, and solidification properties of heavy metals in glass-ceramics were investigated by the controlled heat treatment. The findings indicated that the heat treatment temperature has a significant effect on the distribution and color of heavy metals in glass-ceramic. In the crystallized glass-ceramic, spinel acts as the crystal core for heavy metal solidification, Cr, Cu, and Mn can exist stably in the spinel by the solid solution. The glass-ceramic was expected to be used as a decorative building material.     

陕西某地区饮用水中低浓度重金属的测定及健康风险评价

测定12种生活饮用水样本中的铁、锌、铜、铬、铅、镉6种重金属的浓度,并应用美国环保局推荐的健康风险评价模型对这12种水样中的重金属引起的健康风险做了初步评价。结果表明,在12种生活饮用水中,6种重金属的浓度分别为Fe(0.554 5~2.057 3)×10-4mg/L,Zn(0.002 7~0.455 4)mg/L,Cu(0.002 0~0.021 0)mg/L,Cr(0.001 6~0.010 0)mg/L,Pb(0.008 0~0.014 0)mg/L,Cd(5.217~12.17)×10-5mg/L,通过饮水途径所致健康风险中,4#样的健康风险最高2.13×10-4/a,11#样的健康风险最低2.5×10-6/a。     

淋溶条件下生物炭对矿区土壤中重金属迁移的影响

以玉米秸秆为原料在450℃下制备生物炭,将生物炭按5%的炭土比例施入矿区重金属污染土壤中。通过室内土柱淋溶试验,分析加入生物炭对土壤淋出液pH、重金属纵向迁移行为及重金属累积释放量的影响。结果表明：加入生物炭处理后土壤淋出液的pH显著高于对照处理,说明生物炭可以在一定程度上缓解土壤的酸性。与对照相比,添加生物炭降低了重金属向下层土壤迁移的风险,淋溶后土柱中Pb、Cu、Zn和Mn的纵向迁移量分别降低了65.93%、50.95%、49.29%和30.95%,生物炭对土壤中重金属纵向迁移抑制的顺序为Pb>Cu>Zn>Mn,生物炭对Pb的钝化效果最好。随着淋溶液体积的增加,Pb、Cu、Zn和Mn这4种重金属的淋溶累积释放量总体上呈现出前期快速溶出和后期缓慢溶出两个明显的阶段。4种重金属的累积释放量大小为Pb>Mn>Zn>Cu,添加生物炭后明显降低了重金属的累积释放量。对土壤中金属释放过程进行数学方程拟合后发现,应用Elovich方程能较好地描述重金属释放过程,说明这4种重金属元素在土壤中的淋溶和释放过程的机制不是单一反应过程,而是属于活化能变化较大的复杂反应过程。加入生物炭后各重金属的b值均低于对照组,重金属迁移速率随着生物炭的添加而降低,说明生物炭能提高土壤对重金属离子的吸附力,降低因土壤淋溶作用而引起的重金属迁移,可以实现对重金属复合污染矿区土壤的修复。     

矿渣基草酸钙化学键合材料的制备及其固化重金属的研究

利用富含钙氧化物的高炉矿渣与草酸在常温进行反应制备草酸钙化学键合材料,探究了草酸(OA)和高炉矿渣(BFS)质量比对草酸钙化学键合材料力学性能的影响,以及草酸钙化学键合材料对重金属(Pb、Cd和Cu)的固化效果。结果表明,当草酸和高炉矿渣质量比为0.25时,草酸钙化学键合材料力学性能最优,其在自然养护3 d、7 d和28 d的抗压强度分别为25.70 MPa、27.86 MPa和34.79 MPa。采用XRD和SEM对草酸钙化学键合材料的物相组成和微观形貌进行分析,其主要物相为草酸钙(CaC₂O₄·H₂O),微观结构致密。在重金属(Pb和Cu)掺量为8%(质量分数)时,草酸钙化学键合材料对重金属(Pb和Cu)仍有良好的固化效果,固体浸出毒性质量浓度低于国家标准限值。研究结果为高炉矿渣制备草酸钙化学键合材料提供了参考。     

不同底物浓度下生物淋滤垃圾焚烧飞灰中重金属的动力学研究

通过氧化硫硫杆菌生物淋滤处理城市垃圾焚烧飞灰中的重金属。采用分批摇床培养,研究了生物淋滤过程中,底物浓度(S)对飞灰中重金属去除速率的影响。采用经验方程研究了S浓度对飞灰中重金属去除速率的影响,得到不同S浓度下4种重金属(Cu、Zn、Cd、Pb)的去除速率常数km,其大小顺序为ZnCuCdPb。综合各个动力学参数推知S浓度为5 g/L是本生物淋滤体系的最佳底物浓度。     

生物质固定化硫酸盐还原菌处理废水中重金属离子

采用海藻酸钠和3种生物质载体(稻壳、玉米芯、秸秆)固定化的硫酸盐还原菌(SRB)处理单一重金属(700 mg/L Fe2+, 75 mg/L Cu2+, 120 mg/L Pb2+, 80 mg/L Cd2+)废水,筛选出稻壳为效果较优的固定化载体,并对合成重金属废水(含400 mg/L Fe2+, 30 mg/L Cu2+, 50 mg/L Pb2+, 40 mg/L Cd2+)的处理效果作了进一步研究. 结果表明,稻壳固定化SRB去除单一重金属时,Fe2+, Cu2+, Pb2+, Cd2+去除率分别为99%, 100%, 100%, 100%;处理合成重金属废水时,4种重金属去除率分别为98.06%, 100%, 99.35%, 100%.     

污水污泥页岩烧结制品的重金属固化与水环境浸出稳定性

提高重金属固化程度与浸出稳定性是含重金属污水污泥处置和利用的前提。采用污水污泥并模拟提高其重金属Cr、Cu、Pb的含量,与页岩混合制备烧结砖和陶粒制品,研究重金属在页岩制品高温烧制过程中的固化率以及制品中重金属的水环境浸出稳定性,通过X射线衍射和扫描电子显微镜分析含重金属矿物的赋存形态和页岩制品微观形貌对重金属固化与浸出稳定性影响。与相同条件下焚烧纯污水污泥相比,重金属在页岩制品烧制过程中固化率明显提高,浸出毒性明显降低,重金属在页岩制品中易形成稳定的尖晶石型矿物以及页岩制品所具有的致密微观结构;相比烧结砖,陶粒中重金属固化程度和浸出稳定性更高,因为陶粒在更高温度下有利于尖晶石型矿物和致密结构形成。     

Investigation of stabilization/solidification for treatment of electric arc furnace dust: Dynamic leaching of monolithic specimens

Diffusion-controlled leaching of heavy metals (Cr, Ni, Pb and Zn) from electric arc furnace dust treated with ground granulated blast furnace slag (GGBFS) and with ordinary Portland cement (OPC) was evaluated. Monolithic specimens were evaluated under dynamic leaching conditions for 84 days with periodic leachant renewal. The influence of leaching time, nature of the leachant, binder type and the water/solid ratio of the monoliths were investigated. Results obtained showed both binders can immobilize heavy metals in the monoliths under dynamic leaching conditions, with cumulative quantity of leached metal under 0.138 mg (Cr). Alkaline leachant increased metal release from specimens and reducing the water/solid ratio of the monolith allowed for a decrease in the cumulative mass of metals leached. Chemical and mineralogical characterizations indicated that the metals were evenly distributed throughout the specimens for both binders. Decalcification was observed on the OPC monolith border following leaching. This decrease in Ca corresponded to an altered zone (20 μm), identified by scanning electron microscopy. The GGBFS sample did not show an altered zone.     

Test of electrodialytic upgrading of MSWI APC residue in pilot scale: focus on reduced metal and salt leaching

In this study a pilot plant for electrodialytic treatment of municipal solid waste incineration (MSWI) air pollution control (APC) residue was tested and proposed as a treatment method which can lead to reuse of this otherwise hazardous waste. The pilot plant was developed based on a design that is adapted from conventional electrodialysis, e.g. used in desalination of solutions. The APC residue was treated in a suspension (8 kg APC residue and 80 L tap water) and circulated through an electrodialytic (ED) stack consisting of 50 cell pairs separated by ion exchange membranes. A direct current was applied to the ED stack for removal of heavy metals (As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Zn) and salts (Cl, Na, SO₄) from the APC residue suspension. Different tank designs for mixing the APC residue suspension were tested as well as changing experimental conditions. A part of the raw experimental APC residue was carbonated by reaction with CO₂ under moist conditions prior to electrodialytic treatment. The carbonation alone reduced the leaching of some heavy metals. However, it was not sufficient to reduce the heavy metal or salt leaching to meet the Danish Category 3 guideline levels for waste material reuse and could not stand as a treatment method alone. Leaching of both heavy metals and salts were significantly reduced by the electrodialytic treatment for both the raw and carbonated APC residue. In the electrodialytically treated carbonated APC residue only Cr exceeded the Category 3 levels while in the electrodialytically treated raw APC residue both Pb and Zn leaching exceeded the Category 3. Optimization of the electrodialytic upgrading method is necessary to meet the Category 3 levels for all heavy metals. Removal of Na and SO₄ to below the Category 3 leaching levels were obtained in all the experiments. Cl removal was not sufficient in all experiments even if up to 1 kg of Cl was removed, the optimal conditions for Cl removal was a constant current of 5 A over the ED stack. The results of this study suggest that, with some optimization, electrodialytic upgrading, possibly in combination with carbonation, could be used as a treatment method for MSWI APC residue.     

硅铝调控与晶种诱导对水热稳定飞灰中重金属的协同影响

研究了选取的粉煤灰、膨润土、高岭土、硅藻土作为外源硅铝调理剂添加与雪硅钙石人工晶种诱导对150℃水热法稳定垃圾焚烧飞灰中重金属Pb、Zn、Cu、Cd、Cr的协同影响。飞灰由于富钙而低硅铝的元素特征,导致其在水热条件下无法直接合成沸石类,Pb的浸出浓度仍然超标;当单一或混合添加硅铝调理剂添加量为10%时,其水热产物中有水钙铝榴石或加藤石生成;提高添加量至30%时,均有目标雪硅钙石的生成,这与30%添加量下飞灰中Ca/（Al+Si）元素比接近雪硅钙石的理想元素比值0.67~1.20直接相关。混合添加30%的粉煤灰与硅藻土为最佳选择,水热产物Pb的浸出浓度降低至0.30 mg·L^-1,且在此基础上再添加3%的诱导晶种可加速从第6 h开始即合成雪硅钙石,并使Pb的浸出浓度下降到最低值0.28 mg·L^-1。硅铝调控（30%的复合硅铝调理剂,其中粉煤灰：硅藻土为1：1）与晶种诱导的协同影响下高效生成雪硅钙石,并显著抑制Pb、Zn等在水热过程中向液相的转移、降低其在水热液相中的浓度,使飞灰中的重金属在水热后确实稳定于水热固相产物中而非迁移至水热液相造成污染转移,真正实现了飞灰中重金属的固定化。     

Implementation of Hybrid Inorganic/Organic Adsorbents for Removal and Preconcentration of Heavy Metals from Industrial Waste and Drinking Waters

Three hybrid inorganic/organic adsorbents based on alumina and phenylazoformic acid 2-phenylhydrazide were synthesized, characterized and examined for their heavy metal sorption properties. The main purpose of this research paper is to study and explore the combined hybrid characters of inorganic/organic sorbents for the selective removal and preconcentration of heavy metals via static and dynamic solid phase techniques from industrial wastewater and drinking tap water samples as well. The hybrid inorganic/organic adsorbents were identified as strongly resistive to leaching in solutions with pH 1–7 and thermally stable up to 350°C. Optimization of heavy metal removal by implementation of newly designed hybrid inorganic/organic adsorbents was studied in presence of various factors as the effect of pH of contact solution and reaction time via determination of the metal sorption capacity and distribution coefficient. The hybrid adsorbents were successfully implemented for the selective removal of Pb(II), Cu(II), Fe(III), and Cr(III) from industrial wastewater samples with recovery values in the range of 91–99 ± 2–3% as well as 98–99 ± 1–3% for the selective preconcentration of Pb(II), Cu(II), and Cr(III) from drinking tap water samples without noticeable interference caused by the matrix effect.     

赤泥-磷石膏复合材料中重金属浸出研究

为实现赤泥和磷石膏两大工业固废的资源化利用,采用未经改性处理的赤泥与磷石膏为原料,通过复合助剂的改性固化作用制备达到充填要求的复合材料。当赤泥用量为总原料质量的85%、磷石膏为5%时,复合材料养护28 d的抗压强度为4.34 MPa,达到了矿山充填力学性能要求。参照《固体废物浸出毒性浸出方法水平振荡法》（HJ 557—2010）和《块状废物或建材中无机组分扩散浸出行为测试容器实验》（EA NEN 7375—2004）对颗粒状和块状样品对比进行浸出实验,研究了赤泥-磷石膏复合材料中重金属元素（镉、铬、镍、钡）的浸出行为。结果表明,重金属浸出浓度由大到小依次为铬、钡、镍、镉;磷石膏掺量在5%以内时重金属元素浸出浓度及扩散系数变化较小,超过5%后重金属元素浸出率增加。对两种浸出方法复合材料中重金属元素的浸出行为进行动力学分析,发现重金属元素的浸出行为主要受扩散作用控制,在长期浸出过程中还受到耗竭作用和延滞作用控制。     

重金属离子对蒸养混凝土力学性能影响及其浸出特性研究

蒸养混凝土具有早期强度高、模具周转速度快和生产效率高等显著优势,成为混凝土预制构件主要制备工艺.通过抗压强度、离子浸出试验、X射线衍射等测试方法,研究了锌、铬、铜对蒸养混凝土的力学性能、水化产物结构及其浸出特性,并探讨了粉煤灰对蒸养混凝土固化重金属离子效果的影响规律.结果表明:①Zn、Cr和Cu离子能够在不同程度上降低蒸养混凝土的抗压强度,当掺量为1.0％时,抗压强度分别降低了50.63％、13.23％和99.27％;Zn、Cr和Cu离子不能明显改变水化产物的微观形貌,但是会抑制氢氧化钙(CH)和钙矾石的生成和结晶.②当掺量低于1.0％时,蒸养混凝土对Zn和Cr离子具有很好地固化作用,浸出浓度均小于0.21 mg/L,但是Cu离子的浸出浓度高达0.92 mg/L以上.掺加20％粉煤灰的蒸养混凝土抗压强度会降低5～8 MPa,并不能提高其对重金属离子的固化性能.     

Dense glass-ceramics by fast sinter-crystallization of mixtures of waste-derived glasses

Dense glass-ceramics were obtained by cold pressing and sinter-crystallization of a glass originated from the plasma gasification of municipal solid waste (“Plasmastone”) mixed with recycled soda-lime glass and kaolin clay. The optimum mixture featured 45% Plasmastone/45% soda-lime glass/10% kaolin clay and it was sintered according to a fast heat treatment (30 minutes at 1000°C with heating and cooling rates of approximately 40°C/min), mimicking that of industrial ceramic tiles. The fast treatment avoided extensive crystallization during heating, promoting the viscous flow. In this way, dense glass-ceramics with a water absorption below 0.7% could be produced. The developed tiles presented mechanical properties comparable to those of commercial ceramic tiles. Finally, the environmental impact assessment performed on these materials showed that the leaching of hazardous elements was particularly limited. Microprobe analyses indicated that heavy metals were incorporated in newly formed crystals, consisting mainly of hedenbergite, wollastonite, and iron oxide-rich “islands” surrounded by residual glass. The results show that Plasmastone, combined with recycled soda-lime glass and kaolin clay, may be converted in building materials, with a possible commercial exploitation.