Elution of copper from vermiculite with environmentally benign reagents

For the purpose of remediation of soils polluted by heavy metals, the use of some strong synthetic chelating agents such as ethylenediaminetetraacetic acid (EDTA) has been proposed. However, EDTA would not be considered as the preferential choice for the remediation of soil polluted with heavy metals like copper because of its nonbiodegradability and permanent residence in the natural environment. In the present work, some novel environmentally benign chelating agents, glucosamine hydrochloride, chito-oligosaccharide and -asparaginic-N,N-diacetic acid (ASDA) were screened to find alternatives to EDTA by investigating the elution of copper from vermiculite with these reagents and comparing their effectiveness with EDTA. The effects of suspension contact time, reagent concentration and equilibrium pH of the solution on the removal of copper were examined. A stoichiometric amount of EDTA can quantitatively remove copper in both acidic and neutral conditions. Chito-oligosaccharide was a slightly less-effective reagent under acidic conditions compared to EDTA, and an amount well in excess of stoichiometry is required to achieve the maximum removal of copper from vermiculite. Glucosamine hydrochloride shows a relatively weak ability for the liberation of copper. The elution behavior of ASDA was equivalent to EDTA in acidic and neutral media. It was concluded that ASDA is the best substitute for EDTA because of its similar high complexing ability and superior biodegradability.     

新疆尉犁蛭石矿中金云母/蛭石混层结构研究

蛭石矿中常伴生有金/黑云母结构,云母层的存在严重影响了蛭石矿的性能,现有方法不能充分揭示混层的晶体结构特征和蛭石晶层及金云母晶层含量。本文以新疆尉犁蛭石矿为研究对象,利用X-射线衍射(XRD)和X射线荧光光谱(XRF)研究尉犁蛭石结构和相含量。以XRD强度理论和分子量为基础,建立新型水金云母(金云母-蛭石的1∶1规则间层矿物)的参比强度近似计算方法,研究水金云母分子量变化对于定量相分析结果的影响,并与已有的分晶层方法计算得到的各晶层含量进行系统比较。结果表明新疆尉犁蛭石由24.56%的蛭石和75.44%的水金云母组成;以参比强度为基础的XRD定量分析方法具有结果可靠、分析简单,同时可以获得层状硅酸盐多层次结构信息的优点。     

溶液pH值对不同粒径蛭石吸附Cu2+、Pb2+的影响

研究了蛭石对重金属离子的吸附,并初步探讨了不同粒径的蛭石吸附Cu2 、Pb2 的pH值影响范围。结果表明:pH值是影响蛭石吸附重金属离子的一个重要因素,且蛭石的粒径越小,其pH值的影响范围越大,对于Cu2 的吸附效果明显高于Pb2 。     

Modification of vermiculite by polymerization and carbonization of glycerol to produce highly efficient materials for oil removal

Impregnation and reaction of glycerol (Gly) on the surface of expanded vermiculite (EV) was used to produce a highly efficient absorbent to remove water spilled oils. The vermiculite was impregnated by glycerol containing 1, 2 and 4 mol% of H₂SO₄ at EV/Gly ratios, i.e. 1/1, 1/2 and 1/3, and heated to 380, 580 and 750 °C. SEM, TG, BET specific surface area, and Raman analyses indicated that glycerol at 380 °C forms a polymer layer. At higher temperatures, the polymer decomposed to form porous carbon covering the EV surface. These materials were investigated for the removal of three different oils, i.e. diesel, soybean and engine oil spilled on water. The obtained results showed a remarkable increase on oil removal of 600% compared to the non-modified EV.     

The mineral phase quantification of vermiculite and interstratified clay minerals-containing ores by X-ray diffraction and Rietveld method after K cation exchange

Hydrothermal transformations and weathering are important mineralizing processes in carbonatite-related ores. But the transformation products of mafic minerals, such as the clay minerals, vermiculite and interstratified phases, preclude the use of X-ray diffraction, particularly the Rietveld method, for mineral phase quantification. After treatment with KCl, vermiculite and interstratified phases (all peaks roughly at 1.2, 1.4-1.5 and 2.4 nm) are converted to a phlogopite-like structure with d(0 0 1) = 1.0 nm, which can successfully be refined. The method was tested using three carbonatite-derived ores, with a total phlogopite-like phase content ranging from 1.2 to 32.3 wt.%. Comparison of the chemical analyses with the calculated chemical composition, based on the phase quantification and the mineral composition is in good agreement for major elements, such as Si, Fe and Al. For P results were also very good, but Ti and Nb are generally underestimated, and Ba is overestimated. Minerals with lower contents, as pyrochlore, approach the diffraction detection limit. Problems to accurately determine mineral composition for some of the phases also impacts on the reconciliation. The chemical composition of the pyrochlore group minerals changed, but not to an extent to constrain the usefulness of the technique. Cation exchange successfully extended the amenability of the Rietveld method for phase quantification.     

Carbon nanostructures-modified expanded vermiculites produced by chemical vapor deposition from ethanol

In this work, chemical vapor deposition using ethanol and FeMo catalysts at 600, 700, 800 and 900 °C was used to modify the surface of expanded vermiculite (EV). Scanning electron microscopy, Raman spectroscopy, X-ray diffraction, Mössbauer spectra, N₂-BET surface areas, and carbon elemental analyses suggested that the FeMo catalyst promoted 2–3% growth of carbon in different forms, mainly nanofibers, on the EV surface. The amount of 2–3% carbon produced by ethanol/CVD process on EV produced a 500% increase in the absorption of soybean, diesel and engine oil, with a concomitant decrease on water absorption. These results were discussed in terms of a hydrophobization of the EV surface by the carbon structures and a “sponge-like” effect due to the entangled nanofibers structure, as it was observed by microscopy, and an increase of N₂-BET surface area from 3 m² g⁻¹ for EV up to 21 m² g^–1 for the ethanol CVD-treated EV.     

Understanding the performance of a pilot vermiculite exfoliation system through process mineralogy

This paper reports on the application of process mineralogy to understand the experimental performance of a microwave based system for the exfoliation of vermiculite type minerals. When montmorillonite type clay structures are exposed to high intensity electric fields they expand very rapidly with the degree of expansion being directly related to the applied electric field strength. This basic understanding of the interaction of microwave fields with such materials has been used to develop a pilot scale microwave based process for the exfoliation of vermiculite. During commissioning of the system it was noted that vermiculites from different geographical sources behaved very differently in terms of the achieved expansion ratio. A systematic mineralogical evaluation of these different materials was carried out using Mineral Liberation Analysis (SEM/MLA), Thermo-gravimetric analysis and X-ray Diffraction (XRD) in order to determine the reasons for the variation in performance. Samples from vermiculite mines in Australia, Brazil, China and South Africa were studied. The mineralogy and mineral characteristics such as liberation, size and texture of the samples were quantified for each ore sample. The South African and Australian samples were found to be predominantly hydrated forms of mica. The Brazilian sample was predominantly composed of vermiculite while the Chinese sample was composed almost totally of hydrobiotite. The relationships between the form of hydration and degree of expansion were derived and it is shown that pure vermiculite exfoliates at lower field intensities than the other forms of hydrated mineral. The paper concludes with deductions obtained from the mineralogical assessments of the vermiculites, thereby elucidating the reasons for the performance observed for each feed material in the microwave exfoliation system.     

Mechanical and acoustic absorption properties of lightweight fly ash/slag-based geopolymer concrete with various aggregates

Acoustic absorption and thermal insulation play a key role in modern buildings to make living comfortable and energy-saving. This paper aims to study the workability, physical and mechanical properties, thermal conductivity, and acoustic absorption of modified geopolymer concrete (GPC) with various types of lightweight aggregates (LWA) such as extruded polystyrene foam beads waste (EPS), vermiculite, or lightweight expanded clay aggregate (LECA). The mixtures of geopolymer concrete have been modified by substituting for the ordinary aggregates (dolomite) by volume with various ratios of 0, 25, 50, 75, and 100% for each type of LWA. Besides, the mechanisms of specimens were examined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and mapping. The results illustrated that the compressive strength values range between 8.5 and 47.50 MPa. The hardened density of concrete was between 1500 and 2450 kg/m³, and thermal conductivity was between 0.45 and 1.16 W/m.K. Geopolymer concrete was considered an acoustic absorption and thermally insulating material. Geopolymer concrete was considered an acoustic absorption and thermally insulating material. EPS, vermiculite, and LECA will be beneficial for applications in lightweight geopolymer concrete due to their capability to reduce weight and excellent thermal conductivity, and the property of improving acoustic absorption. The mechanical results indicated that 25% LECA was the best compared with the ratios of other LWA and gained 35.0, 2.7, and 4.3 MPa of compressive, splitting tensile and flexural strength, respectively. It had positive workability; the thermal conductivity was 1.1 W/m.K, and hardened density was decreased to 10% compared to the control. In addition, LECA is considered the superior and suitable material for acoustic absorption compared with other aggregates.     

Catalytic growth of carbon nanotubes and nanofibers on vermiculite to produce floatable hydrophobic “nanosponges” for oil spill remediation

In this work, chemical vapour deposition (CVD) synthesis of carbon nanotubes (CNT) and nanofibers on the surface of expanded vermiculite (EV) was used to produce a highly hydrophobic floatable absorvent to remove oil spilled on water. XRD, SEM, TG and Raman spectroscopy showed that the carbon nanotubes and nanofibers grow on FeMo catalyst impregnated on the EV surface to form a “sponge structure”. As a result of these carbonaceous nanosponges the absorption of different oils remarkably increased ca. 600% with a concomitant strong decrease of the undesirable water absorption.     

Hydration properties of vermiculite in phenolic resin friction composites

The dehydration and rehydration properties of the Mg-vermiculite are strongly affected by their crystal structure. Changes in the structure of Mg-vermiculite after dehydration and rehydration were used for evaluation of dehydration properties of composite materials containing vermiculite and phenol formaldehyde resin during friction process and for estimation of temperature on the surface of composite. From XRD patterns follows that d-spacing of the first basal diffraction varies as a function of applied annealing temperature and Mg-vermiculite alone rehydrates if the heating temperature does not exceed 700 °C. If embedded in a phenolic resin matrix, rehydration ability of vermiculite is limited and depends on vermiculite/resin content ratio. The maximum detected temperature on the friction surface of investigated composite samples after friction test was 900 °C.