酸浸出法回收冶金污泥中的有价金属

采用二次酸浸出的方法回收镍钴湿法冶金工业污泥中的有价金属。先采用水和硫酸作为浸出剂浸出Mg和Na,最佳工艺条件为浸出液的pH 7.5、浸出时间5 min、浸出剂体积与干污泥质量的比(ω)为10 mL/g。再采用硫酸作为浸出剂、焦亚硫酸钠作为还原剂进行二次酸浸,在硫酸与污泥质量比为1.3、焦亚硫酸钠与污泥质量比为0.3、ω为5 mL/g、浸出温度85℃、浸出时间20 min的最佳工艺条件下,Co、Ni、Cu、Mn和Zn的浸出率分别达92.45%、93.48%、89.52%、97.78%和94.79%。经XRD表征,浸出后污泥中未见原污泥中的矿物相,说明原污泥中的矿物几乎全部被溶解。     

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn–C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2 M H₂SO₄, 1 h, 80 °C).     

Hydration and leaching characteristics of cement pastes made from electroplating sludge

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the ²⁹Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, including nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic β-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability.     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.     

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.

     

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.     

Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

Effect of compost treatment of sewage sludge on nitrogen behavior in two soils

This work aims to evaluate the effects of compost treatment of digested sewage sludge on nitrogen behavior in two soils, a Spodosol and an Oxisol soil. Digested sewage sludge was composted with sawdust and woodchips, diluting the total nitrogen to one-fourth (dry mass basis) of its original value. Then, sludge and compost were added to the two soils on an equivalent dry weight basis to consider the risk of NO3- -N leaching. Compost treatment of sewage sludge has slowed down the release of mineral-N to half in the Spodosol and to one-third in Oxisol soil. As a result, NO3- -N concentrations in soils incubated with compost were less than half of the amounts found from soils incubated with digested sludge. Estimates were made of the maximum monthly nitrate to leach from the four combinations of soil and sludge treatment. Application of digested sludge, at a higher nitrogen application rate, resulted in a higher nitrate leaching potential than application of the compost product. Soil type also played an important role, with the Oxisol having slightly higher estimated leaching potential than the Spodosol. The higher nitrate release rate in the Oxisol is counterbalanced by its higher field capacity to lessen the expected difference between the two soils.     

Impacts of ultrasound on selective leaching recovery of heavy metals from metal-containing waste sludge

Lab synthesized metal-bearing sludge (LSMS) was used in series of designed lab tests to evaluate impacts of ultrasound on selective separation of heavy metals through acid leaching. The tests eliminated the potential of induced bias generated by utilizing field sludge that were produced from different location sources. The results showed that metal pairs of Cu and Fe, Cu and Cr, and Cr and Fe inside LSMS could be practically separated with one metal being contained in a liquid phase and another in a solid phase through acid leaching processes enhanced by ultrasound. With assistance of ultrasound, the acid leaching demonstrated a more efficient segregation between metals within LSMS than a conventional leaching that doesn’t have ultrasonic enhancement, and the tests provided in a generic means that ultrasonically enhanced acid leaching could cost-efficiently recover heavy metals from metal-containing waste sludge.     

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.     

Bioleaching of zinc and aluminium from industrial waste sludges by means of Thiobacillus ferrooxidans

Biological solubilisation of heavy metals contained in two different kinds of industrial wastes was performed in batches employing a strain of Thiobacillus ferroxidans. The wastes tested were: a dust coming from the iron-manganese alloy production in an electric furnace (sludge 1) and a sludge coming from a process treatment plant of aluminium anodic oxidation (sludge 2). The experimental results pointed out the ability of the used strain to maintain the environment, that initially has a pH about 8, at strongly acid conditions (pH 2.5-3.5), producing sulphuric acid that is the chemical agent responsible for the metals solubilisation. At wastes initial concentration of 1%, the percentage of solubilised metals was 76 and 78% for the wastes 1 and 2, respectively, but the lag phase was considerably longer for sludge 2 than for sludge 1, indicating a different affinity of microorganisms for the solid phase. Increasing the initial slurry concentration, the percentage of removed metal reached 72-73% for the sludge 1, while in case of sludge 2, the total amount of solubilized metal progressively decreased. Two kinetic models are proposed to describe the trends of metals solubilization curves.     

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.     

氨基磺酸溶液浸出废锂离子电池负极活性材料中的锂

随着锂离子电池的广泛应用,产生了大量废锂离子电池,其负极活性材料中积累了高品位的锂。锂作为一种稀有金属,对其进行回收利用很有意义。选取了无毒、稳定性好的氨基磺酸作为浸出剂,浸取废锂离子电池负极活性材料中的锂,考察了预处理方式对负极活性材料成分和结构的影响以及浸出条件对锂浸出率的影响。结果表明:600℃下煅烧4 h,可完全去除附着在负极活性材料表面的有机物;在氨基磺酸浓度0.75 mol/L、固液比5 g/L、浸出温度40℃、浸出时间45 min的最佳浸出条件下,负极活性材料中锂浸出率达97.2%。     

Evaluating the biogas potential of the dry fraction from pretreatment of food waste from households

At the waste handling company NSR, Helsingborg, Sweden, the food waste fraction of source separated municipal solid waste is pretreated to obtain a liquid fraction, which is used for biogas production, and a dry fraction, which is at present incinerated. This pretreatment and separation is performed to remove impurities, however also some of the organic material is removed. The possibility of realising the methane potential of the dry fraction through batch-wise dry anaerobic digestion was investigated. The anaerobic digestion technique used was a two-stage process consisting of a static leach bed reactor and a methane reactor. Treatment of the dry fraction alone and in a mixture with structural material was tested to investigate the effect on the porosity of the leach bed. A tracer experiment was carried out to investigate the liquid flow through the leach beds, and this method proved useful in demonstrating a more homogenous flow through the leach bed when structural material was added. Addition of structural material to the dry fraction was needed to achieve a functional digestion process. A methane yield of 98 m³/ton was obtained from the dry fraction mixed with structural material after 76 days of digestion. This was in the same range as obtained in the laboratory scale biochemical methane potential test, showing that it was possible to extract the organic content in the dry fraction in this type of dry digestion system for the production of methane.     

Improving hydrolysis of food waste in a leach bed reactor

This paper examines the rate of degradation of food waste in a leach bed reactor (LBR) under four different operating conditions. The effects of leachate recirculation at a low and high flow rate are examined with and without connection to an upflow anaerobic sludge blanket (UASB). Two dilution rates of the effective volume of the leach bed reactors were investigated: 1 and 6 dilutions per LBR per day. The increase in dilution rate from 1 to 6 improved the destruction of volatile solids without connection to the UASB. However connection to the UASB greatly improved the destruction of volatile solids (by almost 60%) at the low recirculation rate of 1 dilution per day. The increase in volatile solids destruction with connection to the UASB was attributed to an increase in leachate pH and buffering capacity provided by recirculated effluent from the UASB to the leach beds. The destruction of volatile solids for both the low and high dilution rates was similar with connection to the UASB, giving 82% and 88% volatile solids destruction respectively. This suggests that the most efficient leaching condition is 1 dilution per day with connection to the UASB.     

Evaluation of heavy metal leaching from spent household batteries disposed in municipal solid waste

Batch leaching tests and simulated landfill lysimeter tests were performed to evaluate the contents of heavy metals leached from spent batteries in the municipal solid waste. The toxicity characteristic leaching procedure was utilized to perform the batch leaching tests of 36 spent batteries. Four lysimeters were prepared with battery contents ranging from 0% to 100% by weight for column tests, and the experiments were performed at ambient temperature. The age of all the batteries used in the study ranged from freshly disposed up to approximately 3 years old. The results from the batch tests showed that the type of battery influenced the heavy metal concentrations in the leached solutions. The lysimeter experiment results illustrated that at lower pH levels more metals are leached than at higher pH levels. The increasing amount of batteries disposed in landfills can contribute to the leaching of more metals, especially Mn and Zn, into the environment. These results indicate that the direct disposal of spent household batteries into a MSW landfill can increase the heavy metal contents in the landfill leachate.     

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.

     

IC反应器处理MTO废水的中试研究

中试研究了内循环(IC)反应器处理甲醇制烯烃(MTO)废水的启动和运行过程,同时考察了颗粒污泥的性状及沼气产量的变化情况。试验过程运行稳定,系统抗冲击性强。以絮状污泥为接种污泥,经过131 d的启动和运行,IC反应器的COD去除负荷可达10 kg/(m~3·d)以上,COD去除率可达90%以上。IC反应器中的成熟颗粒污泥形状规则、密实、粒径大、沉降速率快。IC反应器的沼气产量符合理论预期。     

Laboratory stabilization/solidification of surrogate and actual mixed-waste sludge in glass and grout

Grout and glass formulations were developed for the stabilization of highly radioactive tank sludges. These formulations were tested in the laboratory with a surrogate and with a sample of an actual mixed waste tank sludge. The grout formulation was tested at wet-sludge loadings of 50–60 wt%, giving a volume increase of about 40–50 vol%. Dried sludge was vitrified into glass at waste oxide loadings of 40–50 wt%, giving a volume decrease of about 50–60 vol%. The Resource Conservation and Recovery Act (RCRA) metals included in surrogate testing were Ag, Ba, Cd, Cr, Ni, Pb, Se, Tl and Hg. Since vitrification would volatilize, not stabilize mercury, it was not included in the surrogates vitrified. The actual sludge sample was only characteristically hazardous for mercury by the toxic characteristic leaching procedure (TCLP) but exceeded the Universal Treatment Standard (UTS) limit for chromium. The grout and glass formulations stabilized these RCRA metals within UTS limits. In addition, a grout leachability index of about 9–10 was measured for both ⁸⁵Sr and ¹³⁷Cs, meeting the recommended requirement of >6. The glass leachability index was estimated to be >18 for cold cesium and strontium.     

Immobilization of copper flotation waste using red mud and clinoptilolite

The flash smelting process has been used in the copper industry for a number of years and has replaced most of the reverberatory applications, known as conventional copper smelting processes. Copper smelters produce large amounts of copper slag or copper flotation waste and the dumping of these quantities of copper slag causes economic, environmental and space problems. The aim of this study was to perform a laboratory investigation to assess the feasibility of immobilizing the heavy metals contained in copper flotation waste. For this purpose, samples of copper flotation waste were immobilized with relatively small proportions of red mud and large proportions of clinoptilolite. The results of laboratory leaching demonstrate that addition of red mud and clinoptilolite to the copper flotation waste drastically reduced the heavy metal content in the effluent and the red mud performed better than clinoptilolite. This study also compared the leaching behaviour of metals in copper flotation waste by short-time extraction tests such as the toxicity characteristic leaching procedure (TCLP), deionized water (DI) and field leach test (FLT). The results of leach tests showed that the results of the FLT and DI methods were close and generally lower than those of the TCLP methods.