Phosphate fertilizer from sewage sludge ash (SSA)

Ashes from sewage sludge incineration are rich in phosphorus content, ranging between 4% and 9%. Due to the current methods of disposal used for these ashes, phosphorus, which is a valuable plant nutrient, is removed from biological cycling. This article proposes the possible three-stage processing of SSA, whereby more than 90% of phosphorus can be extracted to make an adequate phosphate fertilizer. SSA from two Swiss sewage sludge incinerators was used for laboratory investigations. In an initial step, SSA was leached with sulfuric acid using a liquid-to-solid ratio of 2. The leaching time and pH required for high phosphorus dissolution were determined. Inevitably, dissolution of heavy metals takes place that would contaminate the fertilizer. Thus in a second step, leach solution has to be purified by having the heavy metals removed. Both ion exchange using chelating resins and sulfide precipitation turned out to be suitable for removing critical Cu, Ni and Cd. Thirdly, phosphates were precipitated as calcium phosphates with lime water. The resulting phosphate sludge was dewatered, dried and ground to get a powdery fertilizer whose efficacy was demonstrated by plant tests in a greenhouse. By measuring the weight of plants after 6 weeks of growth, fertilized in part with conventional phosphate fertilizer, fertilizer made from SSA was proven to be equal in its plant uptake efficiency.     

Calcium phosphate stabilization of fly ash with chloride extraction

Municipal solid waste incinerator by products include fly ash and air pollution control residues. In order to transform these incinerator wastes into reusable mineral species, soluble alkali chlorides must be separated and toxic trace elements must be stabilized in insoluble form. We show that alkali chlorides can be extracted efficiently in an aqueous extraction step combining a calcium phosphate gel precipitation. In such a process, sodium and potassium chlorides are obtained free from calcium salts, and the trace metal ions are immobilized in the calcium phosphate matrix. Moderate calcination of the chemically treated fly ash leads to the formation of cristalline hydroxylapatite. Fly ash spiked with copper ions and treated by this process shows improved stability of metal ions. Leaching tests with water or EDTA reveal a significant drop in metal ion dissolution. Hydroxylapatite may trap toxic metals and also prevent their evaporation during thermal treatments. Incinerator fly ash together with air pollution control residues, treated by the combined chloride extraction and hydroxylapatite formation process may be considered safe to use as a mineral filler in value added products such as road base or cement blocks.     

高纯二氧化锆生产过程中污染的防治

对高纯二氧化锆的生产工艺进行了改革,采用了新型反应器及胶凝除硅,直接酸溶重结晶,直接煅烧等技术,降低了原材料消耗及能耗,减少了废液排放量,并将回收的废物加工成副产品白炭黑,实现了在生产过程中防治污染。     

A new way to stabilize fly ash from municipal incinerators

Heavy metals and toxic chlorinated organics, added to very low grain-size distributions, make fly ashes from municipal incinerators a very hazardous waste. For their disposal, the present general trend is, not only to stabilize chemically the ashes, i.e. to reduce the leachability of the toxic substances, but also to stabilize them mechanically, i.e. to convert them into massive, resistant, and unleachable solids. This paper describes various stabilization methods used on representative European fly ash samples, which led to the development of a new stabilization technique taking place in four stages: elimination of the alkali chlorides by dissolution; addition of a moderate quantity of phosphoric acid; calcination; and solidification with Portland clinker or cement. The principal advantages of the process are as follows: the polychlorodibenzodioxins-polychlorodibenzofurans are destroyed, the reactivity of the heavy metals is reduced drastically, the final solids have satisfactory mechanical properties, and the increase in weight of the waste to be disposed of does not exceed one fourth. Comparative results of TCLP extraction tests are presented.     

硫酸亚铁的综合利用

以工业废弃物硫酸亚铁为原料,加入碳酸氢铵和氯化钾,通过一系列化学反应和过滤、蒸发、煅烧等步骤,可制得硫酸钾、氯化铵、氧化铁红和液态二氧化碳.原料中各主要成分的利用率均达94%以上.     

Steam gasification of epoxy circuit board in the presence of carbonates

To recover useful metals from end-of-life electronic devices and to convert plastic components from these devices into clean fuel gas, steam gasification of epoxy board samples was carried out at 600–700?°C and 0.1?MPa pressure in the presence of a ternary eutectic carbonate (lithium carbonate, sodium carbonate, and potassium carbonate). Hydrogen and carbon dioxide were the main products, and methane and carbon monoxide were detected as minor products. The gasification proceeded in two steps: an initial rapid pyrolysis followed by secondary steam gasification of char produced from the pyrolysis. The ternary eutectic carbonate accelerated not only the latter steam gasification but also the initial rapid pyrolysis. The activation energy for the steam gasification of epoxy board samples in the presence of the carbonate was 122?kJ/mol.     

炭基载体含氧基团对Mn-Ce双金属吸附剂脱硫活性的影响

以无烟煤、烟煤、褐煤以及工业半焦、烟煤半焦为载体,采用超声辅助加压浸渍法制备了Mn-Ce双金属吸附剂。利用固定床装置对吸附剂的烟气脱硫活性进行了评价,并运用BET、XRD和FTIR技术对其进行了表征。结果表明：吸附剂的脱硫活性主要由焙烧后的金属氧化物提供,金属离子本身无脱硫活性;炭基载体中的酯基是影响金属组分脱硫活性的主要因素,酯基在焙烧过程中分解使得金属组分暴露出来,提高了吸附剂的脱硫活性;中等变质程度的烟煤是制备吸附剂的良好载体,含有适量酯基,使得吸附剂表面金属组分分散均匀。     

Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

Ammoniacal leaching and recovery of copper from alloyed low-grade e-waste

The paper concerns a hydrometallurgical method for selective recovery of copper from low-grade electric and electronic wastes. The following consecutive stages were proposed: smelting of the scraps to produce Cu–Zn–Ag alloy, leaching of the alloy in ammoniacal solution, and selective copper electrowinning. Cu–Zn–Ag alloy was a polymetallic and five-phase system. It was leached in chloride, carbonate, sulfate and thiosulfate solutions. This resulted in the separation of the metals, wherein metallic tin and silver as well as lead salts remained in the slimes, while copper and zinc were transferred to the electrolyte. Copper was selectively recovered from the ammoniacal solutions by the electrolysis, leaving zinc ions in the electrolyte. The best conditions of the alloy treatment were obtained in the ammonia–carbonate system, where the final product was copper of high purity (99.9 %) at the current efficiency of 60 %. Thiosulfate solution was not applicable for the leaching of the copper alloy due to secondary reactions of the formation of copper(I) thiosulfate complexes and precipitation of copper(I) sulfide, both inhibiting dissolution of the metallic material.     

Processing of copper converter slag for metal reclamation. Part I: Extraction and recovery of copper and cobalt.

Clean processing of copper converter slag to reclaim cobalt and copper could be a challenge. An innovative and environmentally sound approach for recovering valuable metals from such a slag has been developed in the present study. Curing the slag with strong sulphuric acid, without re-smelting or roasting as practiced currently in the industry, render it accessible to leaching, and more than 95% of cobalt and up to 90% of copper was extracted together with iron by water leaching, leaving silica behind in a residue. The copper in the leach liquor was recovered by cementation with iron and the dissolved iron crystallized as ferrous sulphate monohydrate. The cobalt in the mother-liquor rich in iron was recovered by either cementation or sulphide precipitation. Operation variables in the new process were also investigated and optimized.     

MnO_2陶粒臭氧氧化催化剂的制备及其性能

以凹凸棒土为载体、MnO_2为活性组分,制备了MnO_2陶粒臭氧氧化催化剂,并以草酸为模拟污染物,采用响应面法对催化剂的制备条件进行了优化。实验结果表明:各因素对草酸去除率影响的显著性顺序为MnO_2投加量盐酸溶液质量分数煅烧时间煅烧温度。催化剂的最佳制备条件为:MnO_2投加量200 mg/g,盐酸溶液质量分数20%,煅烧时间2 h,煅烧温度400℃。在初始草酸质量浓度150 mg/L、溶液pH 3.11、臭氧投加量8.10 mg/min、臭氧-氧气曝气量400 m L/min的条件下,最佳条件制备的催化剂在反应30 min时的草酸去除率达66.99%。催化剂具有良好的活性稳定性,且催化过程中Mn~(2+)溶出量低。催化剂具有较大的比表面积,负载的MnO_2类型为α-MnO_2和β-MnO_2。     

Recovery of rare earth elements from waste fluorescent phosphors: Na2O2 molten salt decomposition

In this paper, an efficient recovery of rare earth elements from waste fluorescent phosphors has been reported and the novel process of alkali fusion and acid leaching has been proposed. The experimental results have shown that the key for efficient recycling is the complete dissolution of waste fluorescent phosphors. The Na₂O₂-to-waste mass ratio, calcination temperature and reactive time play considerable roles in rare earth elements extraction during the alkali fusion process. The optimal conditions in terms of temperature, time and Na₂O₂-to-waste mass ratio are 650 °C, 15 min and 2:1, respectively, under which more than 99.5 % rare earth elements are extracted. The possible reaction mechanism of alkali fusion has been proposed.     

我国硫铁矿烧渣综合利用的研究与实践概况

叙述了我国硫酸工业硫铁矿烧渣在水泥助剂、脱硫剂、净水剂、炼铁、剂造铁系化工产品，回收有色金属及贵金属、制砖等多方面综合利用的研究与实践，并结合我国实际情况提出了加强科研成果的推广应用等建设。     

Tannic acid as a novel and green leaching reagent for cobalt and lithium recycling from spent lithium-ion batteries

Tannic acid–acetic acid is proposed as novel and green chemicals for cobalt and lithium recycling from spent lithium-ion batteries through a leaching process. The synergism of both acids was documented through batch and continuous studies. Tannic acid promotes cobalt dissolution by reducing insoluble Co³⁺ into soluble Co²⁺, while acetic acid is critical to improve the dissolution and stabilize the metals in the pregnant leach solution. Based on batch studies, the optimum conditions for metal recovery at room temperature are acetic acid 1 M, tannic acid 20 g/L, pulp density 20 g/L, and stirring speed 250 rpm (94% cobalt and 99% lithium recovery). The kinetic study shows that increasing temperature to 80 °C improves cobalt and lithium recovery from 65 to 90% (cobalt) and from 80 to 99% (lithium) within 4 h at sub-optimum condition (tannic acid 10 g/L). Kinetic modeling suggests the leaching process was endothermic, and high activation energy indicates a surface chemical process. For other metals, the pattern of manganese and nickel recovery trend follows the cobalt recovery trend. Copper recovery was negatively affected by tannic acid. Iron recovery was limited due to the weak acidic condition of pregnant leach solution, which is beneficial to improve leaching selectivity.

     

Heavy metals fractionation before, during and after composting of sewage sludge with natural zeolite

The main limiting factor, in order to use compost in agriculture, is the total concentration of heavy metals. Natural zeolites, such as clinoptilolite, have the ability to take up and remove those metals by utilizing ion exchange. However, it is important to know about the fractionation of the heavy metals during the thermophilic phase and the maturation phase. The purpose of this work was to determine the changes in the fraction of heavy metals in sewage sludge compost in which clinoptilolite is used as a bulking agent to remove metals. The final result indicates that a significant (p < 0.05) percentage of the metals, which is not removed by the zeolite, is associated with the residual fraction which is considered as an inert form.     

木醋调质石灰石煅烧特性试验研究

新型有机钙协同脱硫脱硝技术在实际应用中存在经济代价高的问题,采用木醋废液调质处理石灰石,制得廉价醋酸钙,并对调质产物的煅烧特性进行了研究。X射线衍射分析结果表明,调质石灰石的主要成分为水合醋酸钙,其煅烧过程大致可以分为3个阶段;采用Avrami理论求解调质石灰石的煅烧反应级数,计算结果其反应级数在0.048～0.272较大范围内波动,进一步证明了反应的多阶段性与无定常性。     

Hydrothermal solidification of municipal solid waste incineration bottom ash with slag addition

Hydrothermal solidification of municipal solid waste incineration (MSWI) bottom ash has been carried out under saturated steam pressure (1.56 MPa) at 200 °C for up to 24 h by mixing quartz, slaked lime and water-cooled blast furnace slag (WBFS). The strength enhancement for the WBFS addition was best. The strength development was shown to be due mainly to tobermorite formation, and the tobermorite formation densified matrix, thus promoting the strength development. WBFS seemed to have a higher reactivity than the quartz during the initial hydrothermal process, which provided more silica available to harden the solidified specimens. However, a longer curing time (24 h) was favorable to the quartz dissolution for tobermorite formation, which in turn, enhanced the strength for quartz addition. Curing time affected the crystal morphology evolution, and the stubby plate of tobermorite seemed to result in a high strength enhancement in this study. Laboratory leaching tests were conducted to determine the amount of heavy metals dissolved from the final solidified specimens, and the leaching results showed that after hydrothermal processing the heavy metals dissolved from the solidified specimens were reduced effectively. As such, the hydrothermal processing may have a high potential for recycling/reusing MSWI ash on a large scale.     

Electroremediation part II: A study of the movement of heavy metals during an electroremediation process in Andisol soil

In the Summer 2004 issue of Remediation, the authors presented a study of the influence of buffering behavior in contaminated Andisol soil. This article, Part II, expands on this research by presenting the results of laboratory tests conducted to study the movement of heavy metals in contaminated Andisol soil during the first stage of an electrochemical remediation process. The analysis was performed on the soil after treatment and also on the washing solutions collected during the first four hours. In order to analyze the effectiveness of fast and simple techniques for monitoring the electroremediation process, computer‐aided modeling of speciation in the soil solution was performed in connection with the remediation treatment. The results show that the metals moved mainly as positive species in the soil and later occurred as insoluble forms relative to the pH value in the washing solution from the cathode chamber. © 2005 Wiley Periodicals, Inc.     

硫酸锰渣污染土壤中重金属的形态分布及生物活性

测定了硫酸锰渣污染土壤中Cu,Zn,Cd,Pb,Mn的总量和各形态含量.结果表明重金属总量远超过环境背景值和土壤环境二级标准.重金属各形态分布特征:Cu,有机态>残渣态>铁锰氧化态>碳酸盐态>可交换态;Zn,残渣态>铁锰氧化态>有机态>碳酸盐态>可交换态;Cd,铁锰氧化态>可交换态>碳酸盐态>残渣态>有机态;Pb,铁锰氧化态>残渣态>有机态>碳酸盐态>可交换态;Mn,铁锰氧化态>残渣态>可交换态>有机态>碳酸盐态.重金属的生物可利用性系数和迁移系数均为Cd>Mn>Pb>Cu>Zn.     

Re-cycling of sugar-ash: a raw feed material for rotary kilns

Large amounts of sugar-ash, a material rich in calcium carbonate, are produced as a by-product in the Greek Sugar Industry. This work explores the possibility of re-cycling sugar-ash for use in the lime industry. A representative sample of sugar-ash from the Plati Imathias sugar plant was studied by PXRD, TG/DTG, calcination experiments at temperatures between 650 and 1150 degrees C and experiments to determine the quality of the quicklime produced at temperatures between 850 and 1150 degrees C following methods described in ASTM C110 standard. The sugar-ash was found to consist of 90 wt% calcium rich minerals (calcite and monohydrocalcite) and 10 wt% amorphous material. Traces of quartz were also detected. The quicklime of highest quality was produced at 950 degrees C. It is concluded that this "useless" material (sugar-ash) can be re-cycled for use in rotary kilns in the lime industry at calcination temperatures up to 950-1000 degrees C.