Selective Leaching of Valuable Metals from Waste Printed Circuit Boards

Abstract

This study was carried out to recover valuable metals from the printed circuit boards (PCBs) of waste computers. PCB samples were crushed to smaller than 1 mm by a shredder and initially separated into 30% conducting and 70% nonconducting materials by an electrostatic separator. The conducting materials, which contained the valuable metals, were then used as the feed material for magnetic separation, where it was found that 42% of the conducting materials were magnetic and 58% were nonmagnetic. Leaching of the nonmagnetic component using 2 M H₂SO₄ and 0.2 M H₂O₂ at 85 °C for 12 hr resulted in greater than 95% extraction of Cu, Fe, Zn, Ni, and Al. Au and Ag were extracted at 40 °C with a leaching solution of 0.2 M (NH₄)₂S₂O₃, 0.02 M CuSO₄, and 0.4 M NH₄OH, which resulted in recovery of more than 95% of the Au within 48 hr and 100% of the Ag within 24 hr. The residues were next reacted with a 2 M NaCl solution to leach out Pb, which took place within 2 hr at room temperature.     

Fe3O4／Ag磁性纳米颗粒去除水中的铅离子

采用水相共沉淀法制备小尺寸磁性Fe3O4纳米颗粒，以没食子酸作为还原剂和表面修饰剂，还原Ag[（NH3）2]’制备出Fe3O4／Ag磁性纳米颗粒。研究该磁性纳米颗粒对水溶液中铅离子的吸附行为，研究结果表明，pH为7．0，吸附温度30℃时可得到最好的处理效果，铅的去除率可达99．7％以上，Fe3O4／Ag颗粒吸附行为符合二级动力学模型（R2〉0．99）。该磁性纳米颗粒经过多次再生处理后，仍具有很好的吸附效果，表明Fe3O4／Ag在水处理方面拥有良好的应用前景。     

Selective catalytic oxidation of ammonia over copper-cerium composite catalyst

This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a copper (Cu)-cerium (Ce) composite catalyst at temperatures between 150 and 400 degrees C. A Cu-Ce composite catalyst was prepared by coprecipitation of copper nitrate and cerium nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (500-1000 ppm), the space velocity (72,000-110,000 hr(-1)), the relative humidity (12-18%) and the concentration of oxygen (4-20%) affect the operational stability and the capacity for removing NH3. The effects of the O2 and NH3 content of the carrier gas on the catalyst's reaction rate also are considered. The experimental results show that the extent of conversion of NH3 by SCO in the presence of the Cu-Ce composite catalyst was a function of the molar ratio. The NH3 was removed by oxidation in the absence of Cu-Ce composite catalyst, and approximately 99.2% NH3 reduction was achieved during catalytic oxidation over the Cu-Ce (6:4, molar/molar) catalyst at 400 degrees C with an O2 content of 4%. Moreover, the effect of the initial concentration and reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of less than 92,000 hr(-1).     

Immobilization and volume reduction of heavy metals in municipal solid waste fly ash using nano-size calcium and iron-dispersed reagent

This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO₄-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO₄] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals.

Implications: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.     

A fungal vapor-phase bioreactor for the removal of nitric oxide from waste gas streams.

Ground-level O3 formation is becoming a major concern in many cities due to recent tightening of O3 regulations. To control O3 formation, more efficient treatment processes for O3 precursors, such as NOx and volatile organic compounds (VOCs), are needed. One promising new technology for removing both NOx and VOCs from off-gas streams is biofiltration, a simple process whereby contaminated air is passed through a biologically active packed bed. In this study, a toluene-degrading fungal bioreactor was used to treat an aerobic gas stream contaminated with NO. The fungal bioreactor removed 93% of the inlet 250-ppmv NO at an empty bed contact time (EBCT) of 1 min when supplied with 90 g/m3/hr toluene. The presence of NH4+ concentrations greater than 0.4 mg NH3/g dry packing medium, however, resulted in poor NO removal. The bioreactor achieved a maximum toluene elimination capacity of 270 g/m3/hr and maintained greater than 95% toluene removal efficiencies over the 175-day study period.     

Availability of heavy metals for uptake by Salix viminalis on a moderately contaminated dredged sediment disposal site

Extractability of Cd, Cr, Cu, Ni, Pb, and Zn in a dredged sediment disposal site was assessed using single extraction procedures (H2O; 0.01 M CaCl2; 1 M NH4OAc; NH4OAc-EDTA; CaCl2-TEA-DTPA). Only Cd and Zn were found to exceed statutory threshold values for total content. The field was planted with Salix viminalis "Orm" and accumulation of heavy metals in bark, leaves, roots, and wood was evaluated at seven sampling locations along an observed gradient in texture and pollution. Biomass production was high, ranging from 13.2 to 17.8 t ha(-1) y(-1) dry weight. Metal accumulation in aboveground plant parts was low, amounting to the following annually extracted mass of metals per ha: 5034 g Zn, 83 g Cd, 145 g Cu, 83 g Pb, 12 g Ni and 6 g Cr. The use of accumulating clones and the use of soil amendments might enhance extraction efficiency in future research.     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.     

Electrochemical oxidation of bisphenol A. Application to the removal of bisphenol A using a carbon fiber electrode

Leachate samples with a high strength of ammonium-nitrogen (NH4+-N) were collected from a local landfill site in Hong Kong. Two experiments were carried out to study (1) the inhibition of microbial activity of activated sludge by NH4+-N and (2) the chemical precipitation of NH4+-N from leachate as a preliminary treatment prior to the activated sludge process. The experimental results demonstrated that the efficiency of COD removal decreased from 97.7% to 78.1%, and the dehydrogenase activity of activated sludge decreased from 9.29 to 4.93 microg TF/mg MLSS, respectively, when the NH4+-N concentration increased from 53 to 800 mg/l. The experiment also demonstrated that the NH4+-N in the leachate can be quickly precipitated as MgNH4PO4 x 6H2O after addition of MgCl2 x 6H2O + Na2HPO4 x 12H2O. The NH4+-N concentration was reduced from 5618 to 112 mg/l within 15 min when a molar ratio of Mg2+:NH+:PO4(3-) = 1:1:1 was used. The optimum pH to reach the minimum solubility of MgNH4PO4 x 6H2O was found to be in the range of 8.5-9.0. Attention should be given to the high salinity formed in the treated leachate by using MgCl2 x 6H2O + Na2HPO4 x 12H2O, which may affect microbial activity in the following biological treatment processes. Using two other combinations of chemicals [MgO + 85%H3PO4 and Ca(H2PO4)2 x H2O + MgSO4 x 7H2O] could minimise salinity generation after precipitation, while they were less efficient for NH4+-N removal.     

Long-term operation of a biofilter for simultaneous removal of H2S and NH3

Simultaneous removal of NH3 and H2S was investigated using two types of biofilters--one packed with wood chips and the other with granular activated carbon (GAC). Experimental tests and measurements included analyses of removal efficiency (RE), metabolic products, and results of long-term operation (around 240 days). The REs for NH3 and H2S were 92 and 99.9%, respectively, before deactivation. After deactivation, the RE for NH3 and H2S were decreased to 30-50% and 75%, respectively. The activity of nitrifying bacteria was inhibited by high concentrations of H2S (over 200 ppm) but recovered gradually after H2S addition was ceased. However, the Thiobacillus thioparus as sulfur oxidizing bacteria did not show inhibition at the NH3 concentration under 150-ppm conditions. The deactivation of the biofilter was caused by metabolic products [elemental sulfur and (NH4)2SO4] accumulating on the packing materials during the extended operation. The removal capacities for NH3 and H2S were 6.0-8.0 and 45-75 mg N, S/L/hr, respectively.     

连续流反应器污水硝化过程中的N_2O释放

污水生物脱氮硝化阶段是温室气体一氧化二氮（N2O）的重要释放源。采用连续流反应器在2种进水氨氮（NH4-N,低氮反应器60 mg/L和高氮反应器180 mg/L）浓度条件下驯化硝化菌,并研究了不同初始NH4-N浓度和不同初始亚硝酸盐（NO2-N）浓度条件下所驯化硝化菌释放N2O的特征。结果表明在反应器运行过程中2个反应器释放N2O较少,均小于去除NH4-N浓度的0.01%;N2O的释放均随着初始NH4-N浓度或初始NO2-N浓度的升高而增加;不同初始NH4-N浓度条件下,低氮反应器驯化硝化菌的N2O释放率在0.51%~1.40%之间,高氮反应器驯化硝化菌在0.29%~1.27%之间;不同初始NO2-N浓度条件下,低氮反应器驯化硝化菌的N2O释放率在1.38%~3.78%之间,高氮反应器驯化硝化菌在1.16-5.81%之间。     

Recovering valuable metals from recycled photovoltaic modules

Recovering valuable metals such as Si, Ag, Cu, and Al has become a pressing issue as end-of-life photovoltaic modules need to be recycled in the near future to meet legislative requirements in most countries. Of major interest is the recovery and recycling of high-purity silicon (>99.9%) for the production of wafers and semiconductors. The value of Si in crystalline-type photovoltaic modules is estimated to be ?$95/kW at the 2012 metal price. At the current installed capacity of 30 GW/yr, the metal value in the PV modules represents valuable resources that should be recovered in the future. The recycling of end-of-life photovoltaic modules would supply >88,000 and 207,000 tpa Si by 2040 and 2050, respectively. This represents more than 50% of the required Si for module fabrication. Experimental testwork on crystalline Si modules could recover a >99.98%-grade Si product by HNO₃/NaOH leaching to remove Al, Ag, and Ti and other metal ions from the doped Si. A further pyrometallurgical smelting at 1520ºC using CaO–CaF₂–SiO₂ slag mixture to scavenge the residual metals after acid leaching could finally produce >99.998%-grade Si. A process based on HNO₃/NaOH leaching and subsequent smelting is proposed for recycling Si from rejected or recycled photovoltaic modules.

Implications:The photovoltaic industry is considering options of recycling PV modules to recover metals such as Si, Ag, Cu, Al, and others used in the manufacturing of the PV cells. This is to retain its “green” image and to comply with current legislations in several countries. An evaluation of potential resources made available from PV wastes and the technologies used for processing these materials is therefore of significant importance to the industry. Of interest are the costs of processing and the potential revenues gained from recycling, which should determine the viability of economic recycling of PV modules in the future.     

Natural and pre-treatments induced variability in the chemical composition and morphology of lichens and mosses selected for active monitoring of airborne elements

To enhance the reliability of the moss and lichen transplant technique for active biomonitoring of trace metals in urban environments, we evaluated the natural variability in the chemical composition of the (epilithic and epiphytic) moss Hypnum cupressiforme and the epiphytic lichen Pseudevernia furfuracea from two reference areas in NE Italy. Green shoots of epilithic mosses and lobes of epiphytic lichens from larch branches showed rather homogenous composition and were selected for the exposure in nylon bags. As different physico-chemical pre-treatments are usually applied to selected cryptogamic material before its exposure, we also evaluated the effects of oven-drying at 120 degrees C for 24h, washing in 1N HNO3 solution, and in 0.5% NH4 oxalate solution at 85 degrees C for 15 h on the chemical composition and morphology of water-washed moss shoots and lichen lobes. Pre-treatments remarkably changed the chemical composition of selected materials but not their surface morphology.     

Do tubificid worms influence the fate of organic matter and pollutants in stormwater sediments?

In urban area, management of stormwater leads to the accumulation of polluted sediments at the water-sediment interface of various aquatic ecosystems. In many cases, these sediments are colonised by dense populations of tubificid worms. However, the influence of tubificid worms on the fate of stormwater sediments has never been tackled. The aim of this study was to measure in sediment columns the influence of tubificid worms on sediment reworking, organic matter processing (O(2) uptake and release of NH(4)(+), NO(3)(-), PO(4)(3-), and dissolved organic carbon), release of hydrocarbons and heavy metals, and microbial characteristics. Results showed that tubificid worms increased the release of NH(4)(+), PO(4)(3-), and dissolved organic carbon by 2-, 4-, and 3-fold, respectively. O(2) uptake also increased by more than 35% due to tubificid activity. The increase in the percentages of active bacteria and hydrolytic activity in the presence of worms indicated that the higher sediment respiration was caused by the stimulation of microbial communities. A reduction of the number of sulphate-reducing bacteria in the uppermost layers of the sediment was attributed to the penetration of O(2) due to worm activity. These significant effects of tubificid worms were probably linked to the dense network of burrows, which enhanced the exchange surface between the water column and the sediment. No release of heavy metals and hydrocarbons to the water phase was detected in the sediment columns. Understanding the fate and effect of organic stormwater sediments in the natural environment requires the integration of the role of bioturbation in urban pollution studies.     

Characterization of chemical species in atmospheric aerosols in a metropolitan basin

Ambient PM10 aerosol samples were collected from Taiwan's Taichung metropolitan basin between October 1997 and January 1998, and their chemical characteristics studied. The average mass concentration of PM10 was 109.0 +/- 54.1 microg/m3. Carbonaceous materials, sulfate, nitrate, and ammonium were the most important contributors to the PM10 component. On average, 64% of the PM10 was made up of fine particles. During PM10 episodes, average wind speed was 0.7 m/s and relative humidity was high, 83% on average, probably giving rise to stagnation of air pollutants and their entrapment close to the surface. With relative humidity < 70%, NO3-, NH4+, SO4(2-), carbonaceous materials, and PM10 mass showed high correlation with maximum hourly average ozone (O3M). Variation in atmospheric humidity may affect the gas-to-particle interactions of S and N species. The most significant contribution to PM10 in the Taichung urban basin was from the photochemical formation of secondary aerosols and carbonaceous materials in the atmospheric environment.     

壳聚糖双冠醚的合成及其对金属离子的吸附性能研究

将二苯并16－冠－5氯代乙酸酯冠醚分别接枝到西佛碱型壳聚糖冠醚CT－15C和CT－18C上,制备了1,4－壳聚糖双冠醚CT－15CAC和CT－18CAC,经元素分析、FT－IR红外光谱分析和X－射线粉末衍射分析表征了结构。研究了CT－15CAC和CT－18CAC对Pd^2 、Ag^ 、Pt^4 、Au^3 、Cu^2 、Hg^2 的静态吸附性能,并与CT－15C和CT－18C进行了比较。结果表明,这4种吸附剂对贵金属离子如Au^3 、Ag^ 、Pt^4 、Pd^2 都具有较好的吸附性能,并能在Cu^2 和Hg^2 共存的条件下选择吸附Pd^2 ,而且壳聚糖双冠醚CT－15CAC和CT－18CAC比壳聚糖单冠醚CT－15C和CT－18C具有更好的选择性。     

Nickel speciation of residual oil fly ash and ambient particulate matter using X-ray absorption spectroscopy

The chemical speciation of Ni in fly ash produced from approximately 0.85 wt % S residual (no. 6 fuel) oils in laboratory (7 kW)- and utility (400 MW)-scale combustion systems was investigated using X-ray absorption fine structure (XAFS) spectroscopy, X-ray diffraction (XRD), and acetate extraction [1 M NaOAc-0.5 M HOAc (pH 5) at 25 degrees C]-anodic stripping voltammetry (ASV). XAFS was also used to determine the Ni speciation of ambient particulate matter (PM) sampled near the 400-MW system. Based on XAFS analyses of bulk fly ash and their corresponding acetate extraction residue, it is estimated that > 99% of the total Ni (0.38 wt %) in the experimentally produced fly ash occurs as NiSO4.xH2O, whereas > 95% of the total Ni (1.70 and 2.25 wt %) in two fly ash samples from the 400-MW system occurs as NiSO4.xH2O and Ni-bearing spinel, possibly NiFe2O4. Spinel was also detected using XRD. Acetate extracts most of the NiSO4.xH2O and concentrates insoluble NiFe2O4 in extraction residue. Similar to fly ash, ambient PM contains NiSO4.xH2O and NiFe2O4; however, the proportion of NiSO4.xH2O relative to NiFe2O4 is much greater in the PM. Results from this and previous investigations indicate that residual oil ash produced in the 7-kW combustion system lack insoluble Ni (e.g., NiFe2O4) but are enriched in soluble NiSO4.xH2O relative to fly ash from utility-scale systems. This difference in Ni speciation is most likely related to the lack of additive [e.g., Mg(OH)2] injection and residence time in the 7-kW combustion system.     

Nitrous oxide and dinitrogen emissions from soil under different water regimes and straw amendment

In a laboratory study, soil amended with and without wheat straw (2.8 g kg(-1) soil) was incubated under 70% water holding capacity (WHC), continuously flooded and flooded/drained cycle conditions at 30 degrees C for 51 days. Dinitrogen and N2O evolution and ammonia volatilisation were measured during the incubation. Extractable NH4+-N and NO3--N were determined at the end of the incubation. Entrapped N2, N2O, and dissolved NH4+-N and NO3--N in drainage water were measured in the flooded/drained cycle treatment when the floodwater was drained. The results indicated that N loss through ammonia volatilisation was undetected in all treatments due to the low soil pH value (pHH2O= 5.87) and no air movement. The recovery of urea-15N as N2 was lowest in the continuously flooded treatments (0.75% and 0.96% with and without straw amendment, respectively), highest in the 70% WHC treatments (5.65% and 4.41%, respectively), and intermediate in the flooded/drained cycle treatments (1.79% and 2.65%, respectively). The recovery of urea-15N as N2O was in the same order as that of N2, negligible in the continuously flooded treatments, 0.01% and 0.07% in the flooded/drained cycle treatments, and 1.29% and 2.23% in the 70% WHC treatments, respectively. Peak N2O evolution rates were observed after the floodwater was drained but no substantial evolution was found after the soil was reflooded following drained periods. However, peak N2 evolution rates were observed after the onset of both drainage and re-flooding. Considerable quantities of N2 but no detectable N2O were entrapped in the flooded soil.     

The Southeastern Aerosol Research and Characterization Study, part 3: continuous measurements of fine particulate matter mass and composition

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM2.5) mass is performed using a dried, 30 degrees C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO4(2-) via reduction to SO2; (2) NH4+ and NO3- via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO2, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM2.5 components indicates the need to better understand the continuous composition of the unmeasured "other" category, because it contributes a significant fraction to total mass during periods of high PM2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO2 conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH3 to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Application of coupled thermostatted columns in civil engineering and for leaching heavy metals of wastes from foundry sands and mining industry

For many years, the mining industry at Pachuca Hidalgo, Mexico, has produced silver and gold through a cyanide process. Solid wastes (tailings) of this process have been deposited close to centres of population. Many of the metals in these wastes are dispersed via wind and rain, and can be toxic to flora and fauna. Foundry sands are wastes, produced by the automotive industry, the metallurgy industry and others, which are contaminated with many metals such as Fe, Cr, Zn, Pb, Au Ag, Ti, Ge, Co, As, Al, etc. We have previously patented a process for the extraction of toxic and valuable metals from foundry sands using a thermostatted column. The results of this study indicate that the process and the device could be used for removing heavy metals from tailings. In this research both types of waste (foundry sands and tailings) were leached using four coupled thermostatted columns. The presence of heavy metals in the solid wastes was studied using the ICP-AS technique and scanning electron microscopy, and to study the structure we used X-ray diffraction. After leaching we used the solid wastes (without toxic metals) to produce bricks. The mechanical properties of the bricks were assessed against international standards.     

Characterization and reactivity of natural manganese ore catalysts in the selective catalytic oxidation of ammonia to nitrogen

Natural manganese ore (NMO) catalysts were characterized and tested in the selective catalytic oxidation of ammonia to nitrogen oxides under dilute conditions. Also, the oxidation of ammonia (NH(3)) was carried out using pure MnO(2), Mn(2)O(3) for comparing with the activity. It is found that the activity of NMO was similar to that of MnO(2) at low temperature below 150 degrees C but above this temperature, the activity of these catalysts showed the difference. In the course of NH(3) oxidation, N(2), NO, N(2)O and H(2)O were produced. But the quantity of NO(2) produced in this experiment was negligible. At temperature below 250 degrees C, selectivity into N(2) from NH(3) oxidation was in the order, NMO > MnO(2) > Mn(2)O(3). This is the reverse of activity of these manganese oxides. Also the characterization of NH(3) oxidation was proposed and supported by the effect of space velocity, inlet O(2) and NH(3) concentration. The increase of space velocity remarkably influenced not only the conversion but also selectivity into N(2). The higher the reaction temperature was, the higher the effect of inlet O(2) and NH(3) concentration on the reaction rate was. By introducing NO during NH(3) oxidation reaction, the possibility of NMO as selective catalytic reduction catalyst at low temperature was studied and showed positive results.