用含锌废催化剂制备纳米氧化锌

以含锌废催化剂为原料,经酸浸、除杂、锌粉置换、合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备纳米氧化锌。考察了酸浸工艺硫酸溶液含量和液固比（硫酸与含锌废催化剂的质量比）对锌浸出率的影响,以及煅烧温度对纳米氧化锌质量的影响。实验结果表明：在硫酸质量分数为30%、液固比为5的最佳酸浸工艺条件下,锌浸出率为92%;在最佳煅烧温度为400 ℃的条件下,氧化锌质量分数大于95%,比表面积大于50 m²/g;纳米氧化锌颗粒大小均匀,平均粒径小于50 nm。     

Physical separation,mechanical enrichment and recycling-oriented characterization of spent NiMH batteries

Nickel–metal hydride (NiMH) batteries contain high amount of industrial metals, especially iron, nickel, cobalt and rare earth elements. Although the battery waste is a considerable secondary source for metal and chemical industries, a recycling process requires a suitable pretreatment method before proceeding with recovery step to reclaim all valuable elements. In this study, AA- and AAA-type spent NiMH batteries were ground and then sieved for size measurement and classification. Chemical composition of the ground battery black mass and sorted six different size fractions were determined by an analytical technique. Crystal structures of the samples were analyzed by X-ray diffraction. Results show that after mechanical treatment, almost 87 wt% of the spent NiMH batteries are suitable for further recycling steps. Size classification by sieving enriched the iron content of the samples in the coarse fraction which is bigger than 0.25 mm. On the other hand, the amounts of nickel and rare earth elements increased by decreasing sample size, and concentrated in the finer fractions. Anode and cathode active materials that are hydrogen storage alloy and nickel hydroxide were mainly collected in finer size fraction of the battery black mass.     

Sample preparation and biomass determination of SRF model mixture using cryogenic milling and the adapted balance method

The biogenic fraction of a simple solid recovered fuel (SRF) mixture (80 wt% printer paper/20 wt% high density polyethylene) is analyzed with the in-house developed adapted balance method (aBM). This fairly new approach is a combination of combustion elemental analysis (CHNS) and a data reconciliation algorithm based on successive linearisation for evaluation of the analysis results. This method shows a great potential as an alternative way to determine the biomass content in SRF. However, the employed analytical technique (CHNS elemental analysis) restricts the probed sample mass to low amounts in the range of a few hundred milligrams. This requires sample comminution to small grain sizes (<200 μm) to generate representative SRF specimen. This is not easily accomplished for certain material mixtures (e.g. SRF with rubber content) by conventional means of sample size reduction.This paper presents a proof of principle investigation of the sample preparation and analysis of an SRF model mixture with the use of cryogenic impact milling (final sample comminution) and the adapted balance method (determination of biomass content). The so derived sample preparation methodology (cutting mills and cryogenic impact milling) shows a better performance in accuracy and precision for the determination of the biomass content than one solely based on cutting mills. The results for the determination of the biogenic fraction are within 1–5% of the data obtained by the reference methods, selective dissolution method (SDM) and ¹⁴C-method (¹⁴C-M).     

Solidification and recycling of incinerator bottom ash through the addition of colloidal silica (SiO2) solution

The possibility of using incinerator bottom ash as a substitute for natural aggregates was investigated. Rough, porous surface of bottom ash, which diminishes the strength of solidified products, was improved by colloidal silica solution. As a result, a significant increase of mechanical strength was accomplished by a slight amount of silica (<1 wt% to total). Moreover, pozzolanic reaction was induced in initial cement hydration due to the nano-particle size of about 20 nm in colloidal silica solution. Cylindrical specimens and bricks were prepared from bottom ash added to a colloidal silica (SiO2) solution and cement, and then their compressive strengths were evaluated. Cylindrical specimens showed an increase of approximately 60% in compressive strength when colloidal solution containing 4 wt% silica particles was sprayed onto the bottom ash. The strength of bricks containing colloidal silica was in excess of 20 MPa, which meets the requirement of construction materials. Results of leaching tests based on Toxicity Characteristic Leaching Procedure (TCLP) proved that the solidified bottom ash possessed good chemical stability.     

Liberation characteristic and physical separation of printed circuit board (PCB)

Recycling of printed circuit board (PCB) is an important subject and to which increasing attention is paid, both in treatment of waste as well as recovery of valuable material terms. Precede physical and mechanical method, a good liberation is the premise to further separation. In this study, two-step crushing process is employed, and standard sieve is applied to screen crushed material to different size fractions, moreover, the liberation situation and particles shape in different size are observed. Then metal of the PCB is separated by physical methods, including pneumatic separation, electrostatic separation and magnetic separation, and major metal contents are characterized by inductively coupled plasma emission spectrometry (ICP-AES). Results show that the metal and nonmetal particles of PCB are dissociated completely under the crush size 0.6mm; metal is mainly enriched in the four size fractions between 0.15 and 1.25 mm; relatively, pneumatic separation is suitable for 0.6-0.9 mm size fraction, while the electrostatic separation is suitable for three size fractions that are 0.15-0.3mm, 0.3-0.6mm and 0.9-1.25 mm. The whole process that involves crushing, electrostatic and magnetic separation has formed a closed cycle that can return material and provide salable product.     

New characterisation method of electrical and electronic equipment wastes (WEEE)

Innovative separation and beneficiation techniques of various materials encountered in electrical and electronic equipment wastes (WEEE) is a major improvement for its recycling. Mechanical separation-oriented characterisation of WEEE was conducted in an attempt to evaluate the amenability of mechanical separation processes. Properties such as liberation degree of fractions (plastics, metals ferrous and non-ferrous), which are essential for mechanical separation, are analysed by means of a grain counting approach. Two different samples from different recycling industries were characterised in this work. The first sample is a heterogeneous material containing different types of plastics, metals (ferrous and non-ferrous), printed circuit board (PCB), rubber and wood. The second sample contains a mixture of mainly plastics. It is found for the first sample that all aluminium particles are free (100%) in all investigated size fractions. Between 92% and 95% of plastics are present as free particles; however, 67% in average of ferromagnetic particles are liberated. It can be observed that only 42% of ferromagnetic particles are free in the size fraction larger than 20 mm. Particle shapes were also quantified manually particle by particle. The results show that the particle shapes as a result of shredding, turn out to be heterogeneous, thereby complicating mechanical separation processes. In addition, the separability of various materials was ascertained by a sink–float analysis and eddy current separation. The second sample was separated by automatic sensor sorting in four different products: ABS, PC–ABS, PS and rest product. The fractions were characterised by using the methodology described in this paper. The results show that the grade and liberation degree of the plastic products ABS, PC–ABS and PS are close to 100%. Sink–float separation and infrared plastic identification equipment confirms the high plastic quality. On the basis of these findings, a global separation flow sheet is proposed to improve the plastic separation of WEEE.     

Precious Metals in Municipal Solid Waste Incineration Bottom Ash

Municipal solid waste incineration (MSWI) bottom ash contains economically significant levels of silver and gold. Bottom ashes from incinerators at Amsterdam and Ludwigshafen were sampled, processed, and analyzed to determine the composition, size, and mass distribution of the precious metals. In order to establish accurate statistics of the gold particles, a sample of heavy non-ferrous metals produced from 15 tons of wet processed Amsterdam ash was analyzed by a new technology called magnetic density separation (MDS). Amsterdam’s bottom ash contains approximately 10 ppm of silver and 0.4 ppm of gold, which was found in particulate form in all size fractions below 20 mm. The sample from Ludwigshafen was too small to give accurate values on the gold content, but the silver content was found to be identical to the value measured for the Amsterdam ash. Precious metal value in particles smaller than 2 mm seems to derive mainly from waste of electrical and electronic equipment (WEEE), whereas larger precious metal particles are from jewelry and constitute the major part of the economic value. Economical analysis shows that separation of precious metals from the ash may be viable with the presently high prices of non-ferrous metals. In order to recover the precious metals, bottom ash must first be classified into different size fractions. Then, the heavy non-ferrous (HNF) metals should be concentrated by physical separation (eddy current separation, density separation, etc.). Finally, MDS can separate gold from the other HNF metals (copper, zinc). Gold-enriched concentrates can be sold to the precious metal smelter and the copper-zinc fraction to a brass or copper smelter.     

The effect of the addition of fly ash to municipal digested sludge on its electroosmotic dewatering

Effective handling of municipal digested sludge requires that the product cake have low water content. To this end, we investigated the change in sludge dewaterability after the addition of fly ash to municipal digested sludge, dewatering of which is difficult because of its high organic content. The performance of the dewatering is compared with that of electroosmotic dewatering (EDW) and conventional mechanical dewatering (CMD). Fly ash classified by sieving to the size of 25–75 μm and >75 μm is added to the municipal digested sludge by 10, 20, and 50 wt% by wet base. When adding fly ash particles to municipal digested sludge, dewatering efficiency improved with smaller fly ash particle size and with increase in the amount. When sludge was dewatered using an electroosmotic dewatering method, the dewatering efficiency is improved about 40% by adding fly ash of 25–75 μm particle size with 20 wt% when compared with conventional mechanical dewatering method without adding the fly ash. It is concluded that fly ash particles rich in inorganic material are helpful in the dewatering process when added to municipal digested sludge and EDW is more effective than CDW.     

An overview on the processes and technologies for recycling cathodic active materials from spent lithium-ion batteries

This paper aims to make an overview on the current status and new tendency for recycling cathodic active materials from spent lithium-ion batteries. Firstly, it introduces several kinds of pretreatment technologies, followed by the summary of all kinds of single recycling processes mainly focusing on organic acid leaching and synergistic extraction. Then, several examples of typical combined processes and industrial recycling processes are presented in detail. Meanwhile, the advantages, disadvantages and prospect of each single process, combined process, as well as industrial recycling processes, are discussed. Finally, based on a novel acidic organic solvent, the authors briefly introduce an environmental friendly process to directly recycle and resynthesize cathodic active material LiNi_1/3Co_1/3Mn_1/3O₂ from spent lithium-ion batteries. The preliminary experimental results demonstrated the advantages of low reaction temperature, high separation efficiency and organic solvent cycling and preventing secondary pollution to the environment. This process may be used for large-scale recycling of spent lithium-ion batteries after further study.     

电炉炼锡废渣制备白炭黑

以电炉炼锡废渣为原料,经过酸浸处理去除Fe元素后,再用沉淀法制备白炭黑。探索了制备白炭黑的最佳工艺条件。分别采用XRD、FTIR、SEM及粒度分析等技术表征了白炭黑产品的物相、形貌、粒径及其分布。实验结果表明,制备白炭黑的最佳工艺条件为:Na OH溶液浓度8 mol/L、固液比1∶10(干燥废渣质量与Na OH溶液体积比,g/m L)、搅拌速率300 r/min、反应温度90℃、反应时间6 h。在最佳工艺条件下制备的白炭黑产品中Si O2质量分数达92.8%。表征结果显示,所制备的白炭黑产品是由近似球形的颗粒聚集而成的无定形非晶体水合二氧化硅,粒径为95~200 nm的颗粒约占87.5%。     

Poly(vinyl alcohol-co-lactic acid)/Hydroxyapatite Composites: Synthesis and Characterization

There is a wide range of applications where calcium phosphate and hydroxyapatite (HA) are used as biomaterials, e.g. as synthetic bone grafts, coating on metal prostheses (like hip endoprostheses or dental implants) and drug carriers. In the study, the design and synthesis of composites based on poly(vinyl alcohol-co-lactic acid)/hydroxyapatite (PVA-co-LA/HA) with potential for biomedical applications, they are presented. The hydroxyapatite particles were surface-grafted with l(+)-lactic acid in the presence of manganese acetate as catalyst, resulting in modified hydroxyapatite (HA_m) with improved capacity of bonding, respectively for the preparation of the composite based on PVA-co-LA/HA_m. FT-IR spectra further confirmed the existence of PLA polymer on the surface of HA particles. In synthesis of PVA-co-LA copolymer the different molar ratios PVA/LA (2/1, 1/1, 1/2), toluene/water: 1/2 (as azeotrope solvent mixture) and manganese acetate as catalyst, were used. The composite materials were synthesized in situ with 10 wt% HA, and respectively HA_m (reported to PVA and lactic acid components). The composite materials were characterized by FTIR spectroscopy, thermal analyses (DSC, DTG), ¹H-NMR spectroscopy, particle size distribution and zeta potential.     

Characterization of household waste in Greenland

The composition of household waste in Greenland was investigated for the first time. About 2 tonnes of household waste was sampled as every 7th bag collected during 1 week along the scheduled collection routes in Sisimiut, the second largest town in Greenland with about 5400 inhabitants. The collection bags were sorted manually into 10 material fractions. The household waste composition consisted primarily of biowaste (43%) and the combustible fraction (30%), including anything combustible that did not belong to other clean fractions as paper, cardboard and plastic. Paper (8%) (dominated by magazine type paper) and glass (7%) were other important material fractions of the household waste. The remaining approximately 10% constituted of steel (1.5%), aluminum (0.5%), plastic (2.4%), wood (1.0%), non-combustible waste (1.8%) and household hazardous waste (1.2%). The high content of biowaste and the low content of paper make Greenlandic waste much different from Danish household waste. The moisture content, calorific value and chemical composition (55 elements, of which 22 were below detection limits) were determined for each material fraction. These characteristics were similar to what has been found for material fractions in Danish household waste. The chemical composition and the calorific value of the plastic fraction revealed that this fraction was not clean but contained a lot of biowaste. The established waste composition is useful in assessing alternative waste management schemes for household waste in Greenland.     

Chemical and physical characterization of electrode materials of spent sealed Ni-Cd batteries

The present work aimed at the chemical and physical characterization of spent sealed MONO-type Ni-Cd batteries, contributing to a better definition of the recycling process of these spent products. The electrode material containing essentially nickel, cadmium and some cobalt corresponds to approximately 49% of the weight of the batteries. The remaining components are the steel parts from the external case and the supporting grids (40%) containing Fe and Ni, the electrolyte (9%) and the plastic components (2%). Elemental quantitative analysis showed that the electrodes are highly concentrated in metals. The phase identification achieved by X-ray powder diffraction combined with chemical analysis and leaching tests allowed the authors to proceed with the composition of the electrode materials as following: cathode: 28.7% metallic Ni, 53.3% Ni(OH)2, 6.8% Cd(OH)2 and 2.8% Co(OH)2; anode: 39.4% metallic Ni and 57.0% Cd(OH)2. The morphology of the electrodes was studied by microscopic techniques and two phases were observed in the electrodes: (1) a bright metallic phase constituted of small nickel grains that acts as conductor, and (2) the main hydroxide phase of the active electrodes into which the nickel grains are dispersed. The disaggregation of the electrode particles from the supporting plates was easily obtained during the dismantling procedures, indicating that a substantial percentage of the electrodes can be efficiently separated by wet sieving after shredding the spent batteries.     

Heavy metal content in soil reclaimed from a municipal solid waste landfill

Residues reclaimed from a municipal solid waste (MSW) landfill were characterized for the concentrations of a number of heavy metals. The residue fractions analyzed included a fine fraction (<0.425 mm), an intermediate fraction (>0.425 and <6.3 mm) and a fraction consisting of paper products that could ultimately degrade to a smaller size. The intermediate fraction appeared to be organic in nature, while the fine fraction was more soil-like. In general, the metal concentrations were greatest in the intermediate fraction and lowest in the fine fraction. The effect of sample age on the elemental content was also investigated. The concentrations of several elements were greater in older samples (sample approximately 8 years in age) when compared to newer samples (sample approximately 3 years in age). Limitations associated with the land application of residual soil (composed of the fine and intermediate fractions) were assessed by comparing measured concentrations to regulatory threshold values. In general, most metal concentrations were below regulatory thresholds for use in unrestricted settings. At the concentrations measured, however, several elements might limit reuse options, depending on which regulatory threshold serves as a benchmark. Elevated concentrations of arsenic presented the greatest limitation with respect to common US thresholds while elevated cadmium concentrations presented the greatest limitation when compared to UK thresholds. The source of the arsenic was determined to be the waste, not the cover soil.     

Characterization of MSWI bottom ashes towards utilization as glass raw material

The characterization of the bottom ashes produced by two Portuguese municipal solid waste incinerators (MSWI) was performed with the aim of assessing the feasibility of using this waste as raw material in the production of glass that can be further processed as glass-ceramics for application in construction. Density and particle size distribution measurements were carried out for physical characterization. Chemical characterization revealed that SiO(2), a network glass former oxide, was present in a relatively high content (52-58wt%), indicating the suitability for this waste to be employed in the development of vitreous materials. CaO, Na(2)O and K(2)O, which act as fluxing agents, were present in various amounts (2-17wt%) together with several other oxides normally present in ceramic and glass raw materials. Mineralogical characterization revealed that the main crystalline phases were quartz (SiO(2)) and calcite (CaCO(3)) and that minor amounts of different alkaline and alkaline-earth aluminosilicate phases were also present. Thermal characterization showed that the decomposition of the different compounds occurred up to 1100 degrees C and that total weight loss was <10wt%. Heating both bottom ashes at 1400 degrees C for 2h resulted in a melt with suitable viscosity to be poured into a mould, and homogeneous black-coloured glasses with a smooth shiny surface were obtained after cooling. The vitrified bottom ashes were totally amorphous as confirmed by X-ray diffraction. The results from the present experimental work indicate that the examined bottom ashes can be a potential material to melt and to obtain a glass that can be further processed as glass-ceramics to be applied in construction.     

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.     

Colloids in the mortar backfill of a cementitious repository for radioactive waste

Colloids are present in groundwater aquifers and water-permeable engineered barrier systems and may facilitate the migration of radionuclides. A highly permeable mortar is foreseen to be used as backfill for the engineered barrier of the Swiss repository for low- and intermediate-level waste. The backfill is considered to be a chemical environment with some potential for colloid generation and, due to its high porosity, for colloid mobility. Colloid concentration measurements were carried out using an in-situ liquid particle counting system. The in-house developed counting system with three commercially available sensors allowed the detection of single particles and colloids at low concentrations in the size range 50-5000 nm. The counting system was tested using suspensions prepared from certified size standards. The concentrations of colloids with size range 50-1000 nm were measured in cement pore water, which was collected from a column filled with a highly permeable backfill mortar. The chemical composition of the pore water corresponded to a Ca(OH)2-controlled cement system. Colloid concentrations in the backfill pore water were found to be typically lower than approximately 0.1 ppm. The specific (geometric) surface areas of the colloid populations were in the range 240 m2 g(-1) to 770 m2 g(-1). The low colloid inventories observed in this study can be explained by the high ionic strength and Ca concentrations of the cement pore water. These conditions are favourable for colloid-colloid and colloid-backfill interactions and unfavourable for colloid-enhanced nuclide transport.     

Pyrolysis of municipal plastic wastes II: Influence of raw material composition under catalytic conditions

In this work, the results obtained in catalytic pyrolysis of three plastic waste streams which are the rejects of an industrial packing wastes sorting plant are presented. The samples have been pyrolysed in a 3.5 dm(3) reactor under semi-batch conditions at 440 °C for 30 min in nitrogen atmosphere. Commercial ZSM-5 zeolite has been used as catalyst in liquid phase contact. In every case, high HHV gases and liquids which can be useful as fuels or source of chemicals are obtained. A solid fraction composed of the inorganic material contained in the raw materials and some char formed in the pyrolysis process is also obtained. The zeolite has shown to be very effective to produce liquids with great aromatics content and C3-C4 fraction rich gases, even though the raw material was mainly composed of polyolefins. The characteristics of the pyrolysis products as well as the effect of the catalyst vary depending on the composition of the raw material. When paper rich samples are pyrolysed, ZSM-5 zeolite increases water production and reduces CO and CO(2) generation. If stepwise pyrolysis is applied to such sample, the aqueous liquid phase can be separated from the organic liquid fraction in a first low temperature step.     

Wood Plastic Composite Panels: Influence of the Species,Formulation Variables and Blending Process on the Density and Withdrawal Strength of Fasteners

In this work, the influence of four variable parameters including fiber types (poplar and rice straw), fiber contents (45, 60, and 75 wt%), fiber sizes (20–40 and 40–60 mesh), and blending methods (hot-pressing and extrusion) on the physico-mechanical properties of wood plastic composite panels were studied. Generally, the results showed that each of the above-mentioned parameters had significant effect on the nail and screw withdrawal strength (pull-out load) and density, whereas their interactions did not have highly impressive effects on the properties. All tested properties vary significantly with fiber origin. Composites filled with larger fiber size, produced panels with higher withdrawal strength and density. The effect of blending method on density was maximal. Withdrawal strength values of each sample decreased with increase in fiber loading. The lowest withdrawal strength values of nail and screw were obtained from the samples filled with rice straw. It was found that strength properties of the composites can be improved moderately by adding 45 wt% fiber, 20–40 mesh particle and poplar flour. According to the results, the blending method is a significant variable in the determination of withdrawal strength. Therefore, the blending method can be recommended based on the end product applications.     

钼尾矿制备硅微粉

以钼尾矿为原料,采用酸溶—碳酸钾沉淀法制备硅微粉。考察了反应温度、反应时间、K₂CO₃质量分数对产品中SiO₂质量分数和SiO₂产率的影响。得到的优化工艺条件为：钼尾矿粒径小于74 μm,反应温度50 ℃,反应时间60 min,K₂CO₃质量分数50%。在此工艺条件下,SiO₂产率可达98.92%,产品硅微粉的SiO₂质量分数达98.44%,粒径为100~200 nm,超过中华人民共和国黑色冶金行业标准《不定型耐火材料用二氧化硅微粉》（YB/T 115—2004）中SF96指标（SiO₂质量分数≥96.0%）的要求。