Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

Production of technical grade phosphoric acid from incinerator sewage sludge ash (ISSA)

The recovery of phosphorus from sewage sludge ash samples obtained from 7 operating sludge incinerators in the UK using a sulfuric acid washing procedure to produce a technical grade phosphoric acid product has been investigated. The influences of reaction time, sulfuric acid concentration, liquid to solid ratio and source of ISSA on P recovery have been examined. The optimised conditions were the minimum stoichiometric acid requirement, a reaction time of 120 min and a liquid to solid ratio of 20. Under these conditions, average recoveries of between 72% and 91% of total phosphorus were obtained. Product filtrate was purified by passing through a cation exchange column, concentrated to 80% H₃PO₄ and compared with technical grade H₃PO₄ specifications. The economics of phosphate recovery by this method are briefly discussed.     

Leaching of rare earths from Abu Tartur (Egypt) phosphate rock with phosphoric acid

The leaching of rare earth elements (REEs) from Egyptian Abu Tartur phosphate rock using phosphoric acid has been examined and was subsequently optimized to better understand if such an approach could be industrially feasible. Preliminary experiments were performed to properly define the design of experiments. Afterward, 2⁴ full factorial design was implemented to optimize the leaching process. Optimum REEs leaching efficiency (96.7 ± 0.9%) was reached with the following conditions: phosphoric acid concentration of 30 wt.-% P₂O₅, liquid/solid ratio, mL/g, of 5:1, at 20 °C, and 120 min of leaching time. The apparent activation energy of the dissolution of REEs from phosphate rock using the phosphoric acid solution was -19.6 kJ/mol. D2EHPA was subsequently applied as an organic solvent for REEs separation from the acquired leach liquor. REEs stripping and precipitation were conducted, and finally, rare earth oxides with a purity of 88.4% were obtained. The leach liquor was further treated with concentrated sulfuric acid to recover the used phosphoric acid and produce gypsum with a purity of >95% at the same time. A flow diagram for this innovative cleaner production process was developed, and larger-scale experiments are proposed to further understand this promising approach to comprehensive phosphate rock processing.

     

Comparison of two types of municipal solid waste incinerator fly ashes with different alkaline reagents in washing experiments

In this study, we propose a "washing-calcination-conversion of washed fly ash into cement material with bottom ash" (WCCB) system to reduce the amount of fly ash that must be specially treated so it can be used as raw cement material. Calcium hydroxide (Ca(OH)2) is widely used in air-pollution control devices of incinerators while sodium bicarbonate (NaHCO3) is not. We conducted single-, double-, and triple-washing experiments to compare the washing characteristics of two types of fly ash. Unlike NaHCO3 fly ash, Ca(OH)2 fly ash has almost twice as much washed residue and almost 2.5 times more chlorine after the same washing procedure. After washing once, the washing frequency is also important for NaHCO3 fly ash, while the mixing time and liquid/solid ratio are more critical for Ca(OH)2 fly ash. The use of NaHCO3 is more suitable for the WCCB system.     

Treatment process for MSW combustion fly ash laboratory and pilot plant experiments

Fly ash from combustion of municipal solid waste sometimes contains large amounts of soluble salts, such as NaCl, even though the content of soluble toxic metal compounds is relatively low. Removal of the salts by washing with water has been suggested as a method to increase the stability of this type of ash. In the work presented here, a simple washing process was studied and evaluated. The process includes three steps: leaching with water, filtration and displacement washing. Basic data were obtained in laboratory experiments and used in the construction of pilot plant equipment at a full size fluidized bed boiler, where a side-stream of the cyclone ash was treated. The process was designed to minimize the water consumption while obtaining an effective removal of salts and a stable ash residue. In order to achieve this, recirculation of leaching liquor was used and the displacement washing was adjusted to become close to ideal. The results showed that an ash/water slurry with a liquid to solid ratio as low as 3 could be handled without difficulty in the mixing, pumping and filtration units. Washing of the filter cake at a liquid to solid ratio of 0.5 removed the major part of the remaining dissolved salts in the pore liquid. About 90% of the chloride content was removed from the ash, whereas the contents of Na, K, Ca, Cd, Pb and a number of other minor elements were removed by 10-30%. Before treatment, the results of ash leaching tests were sometimes too high for chloride (2003/33/EC), but the treatment reduced the amount of soluble chlorides to far below the limit values. The leachability of most metals was reduced or unaffected by the ash treatment. For Na, K and Cl, it was less than 10% of the value for the untreated ash. However, the results showed that some ash components may be mobilized by the washing. Antimony is the most important due to its toxicity.     

从废弃镍氢电池负极板中回收稀土金属

通过废弃镍氢电池负极板在稀硫酸中的浸出实验，考察了稀硫酸浓度、稀硫酸体积与废弃镍氢电池负极板质量比（液固比）、浸出时间、搅拌转速等因素对稀土金属（RE）浸出率的影响。通过正交实验确定的最佳浸出条件：稀硫酸浓度为2．5mol／L，液固比为10，浸出时间为60min，搅拌转速为800r／min。在此条件下，RE浸出率为92．50％。基于RE的硫酸盐和无水硫酸钠生成RE复盐沉淀的原理，向稀硫酸浸出废弃镍氢电池负极板后得到的硫酸盐溶液中加入无水硫酸钠，得到RE复盐沉淀，通过正交实验确定的最佳沉淀条件为：溶液pH为2．0，无水硫酸钠与浸出液中RE^3＋的摩尔比为4，反应温度为60℃。在此条件下，RE回收率为94．6％。用X射线衍射仪对RE复盐进行了表征。     

Application of large volume injection GC-MS to analysis of organic compounds in the extracts and leachates of municipal solid waste incineration fly ash

Organic solvent and water extracts of fly ash from a Milan (Italy) municipal solid waste incinerator (MSWI) were analyzed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) with programmable temperature vaporizer (PTV). Using injection volumes of 10-100 microl, typically over a hundred compounds were detected in organic solvent extracts and ca. 35% of them could be tentatively identified from their electron impact ionization mass spectra. A protocol for the determination of the maximum amount of a potential environmental pollutant available for leaching (availability test) was developed for four selected target compounds: pentachlorobenzene (PeCB), hexachlorobenzene (HxCB), o-terphenyl (o-TPH) and m-terphenyl (m-TPH). Key parameters, extraction time and liquid-to-solid ratio (L/S), were studied in more detail. Recoveries of PeCB, HxCB and o-TPH spiked into the fly ash samples at two concentration levels ranged from 38% to 53% for freshly spiked and from 14% to 40% for 40-day aged fly ash. Recoveries of m-TPH were 8% to 11% from freshly spiked and less than 3% from aged spiked fly ash. The native amounts in Milan MSWI fly ash, determined in an interlaboratory exercise using the developed protocol, were 31 ng/g PeCB, 34 ng/g HxCB, 72 ng/g o-TPH and 4.4 ng/g m-TPH. A separate methodology was developed for the determination of compounds extracted from fly ash by water (leaching test). Following 8-h sonication at L/S 20, the leached amounts of PeCB, HxCB and o-TPH were 1.1, 3.1 and 6.0 ng/g fly ash, respectively.     

Water washing effects on metals emission reduction during municipal solid waste incinerator (MSWI) fly ash melting process

This study investigated that water washing effects on the metals emission reduction in melting of municipal solid waste incinerator (MSWI) fly ash. Experimental conditions were conducted at liquid-to-solid (L/S) ratio 10, 20, and 100 for water-washing process and its subsequent melting treatment at 1450 °C for 2 h. The simple water-washing process as a pre-treatment for MSWI fly ash can remove most of the chlorides, leachable salts, and amphoteric heavy metals from the MSWI fly ash, resulting in the washed ash having lowered chlorine content. MSWI fly ashes washed by L/S ratio 10 and above that were melted at 1450 °C produced slag containing relatively high vitrificaton ratio of Cu and Pb. Besides, the vitrification ratios of Na, K, Ca, and Mg in washed MSWI fly ash were also higher than that of MSWI fly ash. The results indicated that washed MSWI fly ash can reduce the emission of metallic chlorides during its subsequent melting treatment.     

Investigation of hydrogen generation from municipal solid waste incineration fly ash

Hydrogen generation from municipal solid waste incineration fly ash was investigated to understand the influences of contacting method, kinds of contact solution, liquid to solid ratio, and particle size distribution of materials. Redox properties of materials and hydrogen generation were also studied. The largest quantity of gas generated in contact with water was 29.1 ml/g-ash, most of which was hydrogen. Fluidized bed fly ash generated more gas than stoker fly ash. In order to calculate the hydrogen generation potential (the maximum quantity of gas generated in contact with water), a novel system using a Y-shaped test tube and NaOH was utilized. This method gives values which are related to the quantity of generated gas in contact with water. A relationship between the aluminum content and hydrogen generation potential was observed, especially for fluidized bed fly ash. The reducing potential of fluidized bed fly ash was higher than that of stoker fly ash. Only fluidized bed fly ash showed a positive correlation between aluminum content and reducing potential, and between reducing potential and hydrogen generation potential. These results suggest that fluidized bed fly ash contains more Al⁰ than stoker fly ash. Received: September 11, 1998 / Accepted: March 19, 1999     

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO₄ can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.     

Chloride extraction for quality improvement of municipal solid waste incinerator ash for the concrete industry.

Coal ash from power stations has long been used successfully in the cement industry as binders in several Portland formulations. This is not the case for municipal solid waste (MSW) ash as chloride concentrations, ranging from 10 to 200 g kg(-1) dry weight in the bottom and fly ash, respectively, exceed the maximum allowable concentration in most cement mixtures. To reduce chloride content in MSW bottom ash, a laboratory investigation was carried out based on the exhaustive washing in tap water. The influence of operative parameters such as temperature, granulometric properties and solid/liquid ratio of extraction was evaluated. In addition to optimization of the mentioned operative parameters for full-scale application, the paper gives preliminary indications on mechanistic aspects of the washing operation.     

粉煤灰的改性及对刚果红的吸附

分别采用沸水浸泡、酸浸、碱浸和加热的方法对粉煤灰进行改性处理，利用FTIR仪和XRD仪对改性粉煤灰的成分和官能团进行了分析，并利用改性粉煤灰对模拟刚果红废水进行脱色。实验结果表明：碱改性粉煤灰中含有大量官能团，以及NaPl型沸石类物质，能够明显提高粉煤灰对刚果红的吸附性能；与活性炭相比，碱改性粉煤灰具有更高的性价比；在初始刚果红质量浓度为20mg/L、碱改性粉煤灰加入量为50g/L的条件下，废水的脱色率可达87.52%；碱改性粉煤灰对刚果红的吸附过程遵循二级反应动力学，较好地符合Langmuir等温式和Freundlich等温式。     

皂素和柠檬酸复合淋洗土壤中的钍

采用振荡淋洗和土柱动态淋洗实验研究了皂素和柠檬酸复合对土壤中钍的淋洗性能。实验结果表明:将质量浓度为20 g/L的皂素与浓度为20 mmol/L的柠檬酸以体积比1∶10配制复合淋洗液对污染土壤中钍的去除效果最佳,淋洗3.0 h,钍去除率为84.98%;准一级动力学方程能更好地描述复合淋洗液对钍的淋洗动力学特征;动态淋洗实验中当复合淋洗液用量为1 600 mL时,钍的累积去除量为73.66 mg/kg;淋洗后土壤中钍的酸可提取态、氧化结合态和有机结合态含量分别减少了79.63%、38.13%和20.34%,残渣态含量变化不大;淋洗后土壤中钍的稳定性增加。     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

Utilization of municipal solid waste incineration (MSWI) fly ash in ceramic brick: product characterization and environmental toxicity

In this study, municipal solid waste incineration (MSWI) fly ash was used as a blending in making ceramic brick based on its characterization and an orthogonal test was performed to determine the optimal mixture ratio of the materials. Besides, the fired bricks made in accordance with the optimal mixture ratio were characterized for performance, phase transformation, microstructure, leaching toxicity of the heavy metals in accordance with GB/T 2542-92 (Detection methods for bricks analysis, China) and by means of XRD, SEM and leaching toxicity analysis. It was found that the optimal mixture ratio of materials (MSWI fly ash:red ceramic clay:feldspar:gang sand) was 20:60:10:10 by mass, and the optimal sintering temperature was 950 °C. Leaching results of heavy metals from sintered bricks were reduced considerably in comparison with those from green bricks prior to sintering process. The results as a whole suggested that utilization of MSWI fly ash in ceramic brick constituted a potential means of adding value.     

Simultaneous recovery of vanadium and nickel from power plant fly-ash: Optimization of parameters using response surface methodology

Simultaneous recovery of vanadium (V) and nickel (Ni), which are classified as two of the most hazardous metal species from power plant heavy fuel fly-ash, was studied using a hydrometallurgical process consisting of acid leaching using sulfuric acid. Leaching parameters were investigated and optimized in order to maximize the recovery of both vanadium and nickel. The independent leaching parameters investigated were liquid to solid ratio (S/L) (5–12.5 wt.%), temperature (45–80 °C), sulfuric acid concentration (5–25 v/v%) and leaching time (1–5 h). Response surface methodology (RSM) was used to optimize the process parameters. The most effective parameter on the recovery of both elements was found to be temperature and the least effective was time for V and acid concentration for Ni. Based on the results, optimum condition for metals recovery (actual recovery of ca.94% for V and 81% for Ni) was determined to be solid to liquid ratio of 9.15 wt.%, temperature of 80 °C, sulfuric acid concentration of 19.47 v/v% and leaching time of 2 h. The maximum V and Ni predicted recovery of 91.34% and 80.26% was achieved.     

酸浸—萃取—沉淀法回收废锂离子电池中的钴

采用酸浸—萃取—沉淀法回收废锂离子电池中的钴。实验结果表明:废锂离子电池在600℃下煅烧5 h可将正极材料上的有机黏结剂与正极活性物质分离;正极活性物质在Na OH溶液浓度为2.0 mol/L、n(Na OH)∶n(铝)=2.5、碱浸温度为20℃的条件下碱浸反应1 h后,铝浸出率达99.7%;已除铝的正极活性物质在硫酸浓度为2.5 mol/L、H_2O_2质量浓度为7.25 g/L、液固比为10、酸浸温度为85℃的条件下酸浸反应120 min,钴浸出率高达98.0%;酸浸液在p H为3.5、萃取剂P507与Cyanex272体积比为1∶1的条件下,经2级萃取,钴萃取率为95.5%;采用H_2SO_4溶液反萃后在硫化钠质量浓度为8 g/L、反萃液p H为4的条件下沉淀反应10 min,钴沉淀率达99.9%。     

废无汞碱性电池极性材料制备锰锌铁氧体磁性纳米颗粒

以硝酸浸取废无汞碱性电池极性材料,再加入硝酸铁及蔗糖生成前驱体,最后通过焙烧制得锰锌铁氧体磁性纳米颗粒。优化了酸浸和焙烧条件,采用FTIR和DTA-TG技术研究了前驱体的形成和热解过程,采用XRD、FTIR、TEM技术和振动样品磁强计对锰锌铁氧体进行了表征。结果表明:废无汞碱性电池极性材料酸浸的最佳条件为H_2O_2加入量3%(w)、液固比10 mL/g、稀硝酸浓度4 mol/L、浸取温度40℃,该条件下浸取10 min锰和锌的浸出率均可达100%;所得前驱体为葡萄糖酸盐,其最佳焙烧条件为焙烧温度450℃、焙烧时间2 h;最佳条件下所得锰锌铁氧体为尖晶石型Mn_(0.5)Zn_(0.5)Fe_2O_4,其颗粒为球形、大小均匀,且磁性能优良。     

粉煤灰-粉煤灰合成沸石对Cs~+的固化

以电厂废弃物粉煤灰为原料、采用碱熔-水热法制备了粉煤灰合成A型沸石(以下简称沸石),再以沸石对溶液中的Cs+进行分离富集,最后在碱激发剂的作用下以粉煤灰和吸附后的沸石制得地聚合物固化体。对固化体的性能进行了评价,并探讨了固化机理。实验结果表明:在吸附温度25℃、初始Cs+质量浓度100 mg/L、固液比10.0 g/L的条件下,沸石对的Cs+的吸附率达98%,比粉煤灰提高了2倍以上;沸石掺量为20%~30%(w)时,固化体的抗压强度符合GB 14569.1—2011要求,固化体中Cs+的42 d浸出率和累计浸出分数均远优于GB 14569.1—2011限值,表现出优异的抗浸出性能。     

Process development for recovery of copper and precious metals from waste printed circuit boards with emphasize on palladium and gold leaching and precipitation

A novel hydrometallurgical process was proposed for selective recovery of Cu, Ag, Au and Pd from waste printed circuit boards (PCBs). More than 99% of copper content was dissolved by using two consecutive sulfuric acid leaching steps in the presence of H₂O₂ as oxidizing agents. The solid residue of 2nd leaching step was treated by acidic thiourea in the presence of ferric iron as oxidizing agent and 85.76% Au and 71.36% Ag dissolution was achieved. The precipitation of Au and Ag from acidic thiourea leachate was investigated by using different amounts of sodium borohydride (SBH) as a reducing agent. The leaching of Pd and remained gold from the solid reside of 3rd leaching step was performed in NaClO-HCl-H₂O₂ leaching system and the effect of different parameters was investigated. The leaching of Pd and specially Au increased by increasing the NaClO concentration up to 10 V% and any further increasing the NaClO concentration has a negligible effect. The leaching of Pd and Au increased by increasing the HCl concentration from 2.5 to 5 M. The leaching of Pd and Au were endothermic and raising the temperature had a positive effect on leaching efficiency. The kinetics of Pd leaching was quite fast and after 30 min complete leaching of Pd was achieved, while the leaching of Au need a longer contact time. The best conditions for leaching of Pd and Au in NaClO-HCl-H₂O₂ leaching system were determined to be 5 M HCl, 1 V% H₂O₂, 10 V% NaClO at 336 K for 3 h with a solid/liquid ratio of 1/10. 100% of Pd and Au of what was in the chloride leachate were precipitated by using 2 g/L SBH. Finally, a process flow sheet for the recovery of Cu, Ag, Au and Pd from PCB was proposed.