Crystal phase separation and microstructure of a thermally treated vitrified solid waste

The vitrification method was used to stabilize a solid industrial waste residue rich in iron and lead oxides. Upon devitrification of the glass products, the effect of batch composition on the ability to produce glass-ceramic materials was investigated by electron microscopy techniques. The crystallization and microstructural evolution of the vitreous products was explored with respect to the annealing conditions. In the course of vitrification, ferric oxide functioned as a glass network former, contributing to the structural integrity of the vitreous matrix. After thermal treatment of the vitrified products, at temperatures determined by differential thermal analysis, Pb₈Fe₂O₁₁, PbFe₁₂O₁₉ and Fe₂O₃ were the dominant crystal phases detected in the glass-ceramic products, the former characterized as a new structure. The distribution of iron and lead oxides among different crystalline phases was found to be the dominant parameter determining the efficiency of lead captivation into the volume of the devitrified products, whereas in glass products lead is diffused in the amorphous matrix.     

Microstructural changes of processed vitrified solid waste products

Toxic lead-rich solid industrial wastes were stabilized by the vitrification method. Vitrification was attained by the addition of SiO₂ and Na₂O as vitrifying and melting agent, respectively. The non-toxic, homogeneous, vitreous products studied in the present work, contain 60 wt.% of solid waste. Products with such a high content of solid waste comprise an economically realistic suggestion, but are easily devitrified in conditions of large-scale production due to the difficulty to achieve rapid cooling conditions in the whole volume of a large piece of stabilized product. Thus, it must be ascertained that the loss of homogeneity is not accompanied with the loss of chemical stability. Differential Thermal Analysis (DTA) was applied in order to inspect the prospect to crystal phase separation. The separated crystal phases were characterized by X-ray diffraction and transmission electron microscopy. Possible devitrification processes are investigated in order to interconnect the microstructure with the chemical stability of the devitrified products.     

Design of a Eutectic Freeze Crystallization process for multicomponent waste water stream

Complex, hypersaline brines originating from the mining and extractive metallurgical industries have the potential to be treated using Eutectic Freeze Crystallization (EFC). Although EFC has been shown to be effective in separating a single salt and water, it has yet to be applied to the complex hypersaline brines that are typical of reverse osmosis retentates in South Africa. This paper focuses on the application of EFC for the purification of a typical brine containing high levels of sodium, chlorine, sulphate and ammonia that cannot be achieved with other separation techniques. The presence of ammonia prevents the application of membrane technology to treat the brine, leaving only cooling or evaporation as other possible options. Evaporation produces a mixed salt that requires further treatment. Modelling tools were applied to describe the phase behaviour of the complex saline systems under different process conditions and were experimentally validated. The results showed that Eutectic Freeze Crystallization could be used to selectively recover the sodium as a sodium sulphate salt. The simulation tools were especially useful in the design and optimisation of the process.     

头孢拉定结晶工艺

考察了不同结晶体系对头孢拉定结晶过程的影响,通过正交试验优化了头孢拉定结晶工艺条件,即水量为头孢拉定质量的2倍,三乙胺和N,N-二甲基甲酰胺体积比为1.2,结晶初始温度30℃,结晶终了温度5℃。结果证明,在此条件下所得产品结晶收率可达92%左右。利用高效液相色谱、电子显微镜对产品进行检测证明产品纯度可达98%以上,粒度分布均匀,晶面完整;同时通过40 ℃储存条件下的化学稳定性试验表明产品稳定性符合药品质量要求。     

间苯二甲腈结晶精制工艺

气相氨氧化法生产间苯二甲腈存在产品纯度低、废水排放量大等问题。文中在实验研究的基础上,从溶剂的溶解特性及结晶提纯效果出发,筛选出了以乙醇和水的复合溶剂为间苯二甲腈的结晶溶剂,通过加热溶解、降温结晶、离心过滤及溶剂回收等工艺过程,精制后的间苯二甲腈纯度(质量分数)可达99.5%以上,满足了国际市场的要求,废水排放量也由每1 000 kg产品40 000 kg降至1 100 kg。     

Retention analysis from vitrified low-activity waste and simulants in a laboratory-scale melter

The Waste Treatment and Immobilization Plant (WTP) will process and stabilize nuclear waste stored in tanks on the Hanford Site. At the WTP, the tank waste will be combined with glass-forming chemicals to make a melter feed slurry that can be vitrified in joule-heated melters. Technetium-99 (⁹⁹Tc), a long-lived radionuclide present in tank waste, is semi-volatile from a glass melt at elevated temperatures. A small laboratory-scale melter system has been designed by PNNL to operate under radioactive conditions, giving it the ability to vitrify actual tank waste and gain information about melter feed processability and the partitioning of components of interest. This study describes two runs performed in a duplicate system with non-radioactive simulants of Hanford tanks 241-AP-107 and 241-AN-105 to gain insight into the relationship between the retentions of ⁹⁹Tc and its non-radioactive surrogate Re while also investigating the effects of increasing the reducing agent such as sucrose during vitrification on processing and the retention of semi-volatile components in the glass product. The results from these runs align with the general trends of greater retention in the glass of Re compared to ⁹⁹Tc and the improved retention in the glass of Re with increased reducing agent.     

Sintered esseneite–wollastonite–plagioclase glass–ceramics from vitrified waste

Dense sintered esseneite–wollastonite–plagioclase glass–ceramics have been successfully prepared from a vitrified mixture of important inorganic waste (Bayer process red mud, fly ash from lignite combustion and residues from the polishing of porcelain stoneware tiles). The enhanced nucleation activity of fine glass powders, favoured by particular oxidation conditions, caused a substantial crystallisation, even in the case of very rapid thermal treatments at 900 °C, which led to remarkable mechanical properties (bending strength and Vickers micro-hardness exceeding 130 MPa and 7 GPa, respectively) and a promising chemical durability.     

Analysis of degradation products in thermally treated TATB

Delineating the chemical composition of TATB (1,3,5-triamino-2,4,6-trinitrobenzene) residues produced from the exposure to abnormal thermal environments should lead to a better understanding of the decomposition paths. Identifying and quantifying each compound in thermally produced residues, monitors which compounds are degrading or forming along the decomposition route, as well as providing input for the kinetic models of those pathways. Here we report the methodology of isolating, identifying, and where possible, quantifying soluble compounds present in solid residues of thermally treated TATB (330 °C for tens of minutes). Samples were extracted with DMSO, separated using chromatography, and quantified using their absorption at 354 nm. Identification of unknown compounds was accomplished using high resolution mass spectrometry. TATB, F1 (diamino-dinitro-benzofurazan), HO-TATB (2,4,6-triamino-1-hydroxyl-3,5-dinitrobenzene), and T4A (1-chloro-3,5-dinitro-2,4,6-triaminobenzene) were trace compounds detected in the unreacted TATB. Ten more compounds that formed in the residues were structurally identified including F2 (amino-nitro-difurazan). Several more compounds were observed but not completely identified. We propose possible structures for the unknowns. Of the compounds formed, F1 was the most abundant compound reaching 4.5 % by weight of the degraded solid sample. Other degradation compounds were estimated to sum to trace levels, well below 1 %. Most compounds were new, having not been detected and identified in previous studies of production grade and thermally aged TATB. Many compounds only reached detectable concentrations after several min of thermal exposure.     

合成龙脑制备片状冰片的结晶工艺研究

为解决传统合成龙脑结晶工艺效率低、周期长、产品成片率过低等缺陷,以120~#汽油作为结晶溶剂,考察投料配比(溶剂与合成龙脑质量比)、结晶温度、长晶空间、结晶时间对合成龙脑制备片状冰片的影响。结果表明:采用梯度降温、提高投料配比、拓展长晶空间及控制超溶解度点前后的降温速率等方法能有效促进晶体片状的形成。实验在结晶瓶中设置隔板,以投料比为1.6,结晶按饱和温度62.5℃至45℃速率0.5℃/h;45℃至35℃速率2℃/h;35℃至25℃速率3℃/h进行梯度降温,结晶时间6 d,所得冰片大小合适,成片率达100%,片状收率74.66%,产品经检测符合冰片质量标准(2010版中国药典)。改进的工艺对传统合成龙脑结晶产品的升级具有启示意义。     

Effect of composition and annealing temperature on the mechanical properties of a vitrified waste

The microhardness and indentation fracture toughness of a vitrified industrial waste, in the form of ash, were characterized by the method of static indentation test. These properties were investigated as a function of composition and thermal treatment conditions. To further understand the influence of the constitutive oxides, additional measurements were made in a series of synthetic products, where a mixture of iron and lead oxides was used as a substitute for the ash. The underlying deformation mechanisms controlling the mechanical properties of such complex systems as determined by static indentation tests are discussed. It was found that plasticity, in the amorphous products, is mainly governed from the silica content, even in the cases where silica is not found in sufficient quantity in order to build an extended three-dimensional vitreous network. On the other hand, the morphology of the separated crystalline phases is the dominant factor affecting plasticity in the glass-ceramic products.     

Structural and chemical properties of thermally treated geopolymer samples

This article presents the results of the compositional, structural and morphological study of geopolymers synthesized from metakaolin and an alkali activator. The study involved the investigation of the structural and chemical properties of the geopolymer, in addition to thermally treated geopolymers up to 600 and 900 °C. The precursor of the geopolymer, and the geopolymer samples before and after the thermal treatment, were investigated by Fourier transformation infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and SEM analysis. The corrected average value of the ratio of silicon and aluminum in the geopolymer samples (Si_GP:Al) is about 1.46, which suggests that the obtained geopolymer samples represent a mixture of roughly equal amounts of sialate and sialate-siloxo units. Annealing the geopolymer samples at 600 °C decreases the amount of Si-ONa bonds and induces the cross-linking of polymer changes. At the same time, other sodium containing alumino-silicate phases are created. The thermal treatment at 900 °C leads to a considerable reduction of oxygen and particularly sodium, followed by significant morphological changes i.e. formation of a complex porous structure. Additionally, a new semicrystaline phase appears. Both XRD and XPS results imply that this new phase may be nepheline and it is plausible that this phase begins to nucleate at temperatures below 900 °C.     

Optical properties and orientation of thermally treated acrylic fibers

Acrylic fibers containing methyl acrylate copolymer have been thermally treated in the temperature range 473°–573°K in an inert, oxygen-free environment. The optical properties and an x-ray diffraction orientation parameter have been studied in these fibers, with special attention to correlation with the essential chemical reactions and to the behavior of polymer chain orientation. Densification of the fibers, illustrated by specific gravity and refractive index changes during the thermal treatment, is interpreted as a more efficient packing of the polymer chains in addition to the development of more highly refractive and dense chemical species. An extrapolated value of refractive index of 1.70 for 100% nitrile polymerization supports the presence of naphthyridine structures. Birefringence changes from ?0.003 to +0.27 imply a high degree of retention of the preferred orientation of polymer chains, despite the severe change in the chemical identity of the chains. The contrary behavior of the orientation parameter from the 100 arc of the x-ray diffraction of polyacrylonitrile as the thermal treatment proceeds indicates that the residual polyacrylonitrile sequences have reduced orientation.     

Oxygen evolution reaction on thermally treated iridium oxide films

The properties of electrochemically grown and thermally treated oxide films on iridium were examined by cyclic voltammetry and potentiostatic polarization at potentials of the oxygen evolution reaction in 0.5 mol dm^–3 sulphuric acid. The oxide was grown by square wave pulses from –0.25 to +1.25 V vs SCE, a procedure much faster in comparison with potentiodynamic activation at the same frequency. The activated electrode, exhibiting low corrosion resistance during oxygen evolution, was subsequently stabilized by heat treatment. Optimal conditions between stability and electrocatalytic activity have been determined to be between 200 and 300°C.     

Crystallization process optimization using artificial neural networks

This paper presents a new procedure for optimization of continuous mixed suspensionmixed product removal (MSMPR) crystallizing systems. Owing to the difficulties of theoretical modelling, simulation of the MSMPR crystallization process is based on the use of artificial neural networks (ANN). The optimization criterion is a compound objective function corresponding to an intended mean crystal size dimension and a minimal dispersion. The presence of multiple local minima has called for investigation by several optimization techniques. Ultimately, Luus' and Jaakola's random adaptive method proved to be most effective. The results obtained lend support to the general procedure proposed.     

制备碳酸锂结晶的工艺优化

主要针对含锂卤水通过氯化锂与碳酸钠反应结晶制备高纯度碳酸锂过程中存在的结晶问题做了实验研究。通过考察反应结晶初始浓度、反应温度、进料速率、晶种用量、搅拌速率、进料浓度以及添加剂等对碳酸锂产品的平均粒度及晶体形貌的影响,优化了反应结晶制备碳酸锂的工艺参数。研究表明：在不同优化参数的作用下,通过调控碳酸锂的反应结晶过程,可改变碳酸锂晶体的形貌、粒度及固液分离效果。     

Adsorption of diuron on mechanically and thermally treated montmorillonite and sepiolite

The effects on montmorillonite (Mt) and on sepiolite (Sep) of mechanical (60 and 180 s grinding time) and further thermal treatments (TT) at 500 °C during 24 h, for removing diuron from aqueous solutions were evaluated. The adsorbents and complexes formed were characterised. The specific surface area (SSA), SEM, XRD and zeta potential of the clay mineral samples were determined. The SSA values showed an increase of 50% for ground Mt and a slight decrease for ground Sep. TT reduced SSA by 50% for the Sep samples, but similar values remained for the Mt samples. Both minerals showed a decrease in crystallinity with increasing grinding time and TT. The zeta potential showed an increased of the negative surface charge for the Mt ground samples, but no changes were noticed for the Sep ground samples. The Mt-TT samples showed a slight decrease whilst the Sep samples showed an increase of the negative surface charge in comparison to those without thermal treatment. The adsorption of diuron on Mt was lower than on Sep, and it decreased slightly after 60 and/or 180 s of grinding, despite the larger SSA values. This differences on the adsorption extent were probably due to the increased micropore surface. In contrast, thermal activation caused significantly increased adsorption, especially for the 180-s ground sample that was inversely correlated with the micropore surface, indicating that diuron was not adsorbed in micropores. Diuron adsorption on Sep was higher than on Mt due to its higher SSA. The adsorption capacity of Sep samples was increased by mechanical treatments (ground and sonicated). Moreover, thermal activation led to additional increases in adsorption probably due to changes in the Sep structure by the loss of OH structural groups leading to a more hydrophobic surface. Diuron adsorption on Mt-TT samples produced an increase in the negative surface charge compared to the original sample, whereas a decrease in the negative surface charge was observed for Sep.