Effects of seawater-neutralised bauxite refinery residue on properties of concrete

Various industrial by-products, such as fly ash, ground granulated blast-furnace slag and silica fume, have been used in concrete to improve its properties. This also enables any environmental issues associated with their disposal. Another material that is available in large quantities and requiring alternative methods of disposal is the Bauxite Refinery Reside (BRR) from the Bayer process used to extract alumina from bauxite. As this is highly caustic and causes many health hazards, Virotec International Ltd. developed a patented technology to convert this into a material that can be used commercially, known as Bauxsol™, for various environmental remediation applications. This use is limited to small quantities of seawater-neutralised BRR and hence an investigation was carried out to establish its potential utilisation as a sand replacement material in concrete. In addition to fresh properties of concrete containing seawater-neutralised BRR up to 20% by mass of Portland cement, mechanical and durability properties were determined. These properties indicated that seawater-neutralised BRR can be used to replace natural sand up to 10% by mass of cement to improve the durability properties of concrete without detrimentally affecting their physical properties. Combining these beneficial effects with environmental remediation applications, it can be concluded that there are specific applications where concretes containing seawater-neutralised BRR could be used.

Absorção de gases da queima de combustíveis fósseis em torre de recheio estruturado utilizando lama vermelha

A produção de alumina pelo processo Bayer produz de 1 a 3 toneladas de resíduo por tonelada de alumínio. Esse resíduo é denominado lama vermelha, composto de minerais não solúveis em hidróxido de sódio concentrado, como hematita e outros óxidos férreos, quartzo e óxidos de titânio. A lama vermelha possui em sua composição variados teores de NaOH, dependendo especificamente da planta industrial utilizada. A proposta desse trabalho é avaliar o processo de absorção de gases provenientes de uma caldeira em contracorrente com uma suspensão de lama vermelha a 27%, em torre spray e em torre de recheio estruturado. Foram realizados experimentos variando-se o tipo de torre de absorção, temperatura da fase líquida e teor de sólidos na fase líquida para avaliar a redução do teor dos gases de combustão na saída da torre de absorção e a variação do pH de acordo com o tempo de operação, para que fosse possível identificar o tempo necessário para que ocorra a neutralização da lama vermelha, bem como a redução no teor de dióxido de carbono, para isso foram realizadas medições dos teores de gases na entrada e na saída da torre de recheio estruturado, bem como medições de temperatura e pH. A absorção de CO₂ presente no gás de combustão pela suspensão de lama vermelha se dá pelo processo da carbonatação, no qual o gás reage com o NaOH presente na lama vermelha, sendo a água o catalisador. Os resultados obtidos após os experimentos foram satisfatórios, e concluiu-se que o processo realizado nas torres de absorção é eficiente para a diminuição do pH da lama vermelha e a redução do teor de CO₂ liberado para a atmosfera, promovendo um ganho duplo para o meio ambiente.

Estudo e avaliação do uso de resíduos do processo Bayer como matéria-prima na produção de agregados sintéticos para a construção civil

A grande quantidade de resíduos sólidos, oriundos da indústria de mineração e metalurgia, constitui um sério problema sócio-ambiental. As características físicoquímicas destes resíduos despertam grande interesse para outras indústrias. A indústria cerâmica pode ser uma interessante consumidora da maioria deste material, para suprir a grande escassez das reservas de matérias-primas atual. Neste contexto, este trabalho mostra os estudos realizados para a reciclagem da lama vermelha, como matéria-prima na produção de agregado sintético, visando à construção civil. A lama vermelha, principal rejeito industrial da fabricação de alumina, mostrou-se um insumo de grande interesse na fabricação de diferentes tipos de agregado para ser utilizado na produção de concreto, para a construção civil. Pelas suas características físico-químicas e a grande quantidade que é produzida anualmente (cerca de 10.000.000 t em duas fábricas, só no Norte do Brasil). Estudos realizados neste trabalho mostram a possibilidade de fabricação de agregados, com diferentes propriedades e possibilidades de aplicação, na indústria da construção civil. Estas propriedades dependem do controle de parâmetros, como o teor de sílica livre e argila, a granulometria e a temperatura de sinterização. Tais variáveis permitem controlar perfeitamente a formação de fase vítrea que é a responsável pelas propriedades dos agregados como: porosidade, resistência mecânica e densidade. Este material pode ser utilizado em concreto convencional ou em concretos especiais, para atender a demanda da construção civil.

Concretes with red mud coarse aggregates

Red mud (RM) is a mineral waste, residue of the Bayer process used to obtain alumina from bauxite. While the exploration of rolled pebble damages the environment and is much more controlled by the government, the huge RM disposal areas do not stop increasing and polluting soil, rivers and groundwater sources in Amazon. In this work, the material mixtures used to produce coarse aggregates presented up to 80% of RM, 30% of metakaolin and 30% of active silica as recycled waste. Several tests were carried out to determine the aggregates physical properties and to evaluate the mechanical performance of the concretes with the new aggregates, including hydraulic abrasion strength, and the results were compared to the reference ones, i.e. rolled pebble concretes. Additionally, the sintering process neutralizes any toxic substance as occur in some RM products like tiles and bricks, and these results have encouraged an industrial or semi-industrial production of RM aggregates for concretes.

Construction and analysis of a metagenomic library from an enhanced biological phosphorus removal biomass

The enhanced biological phosphorus removal (EBPR) process is regularly used for the treatment of wastewater, but suffers from erratic performance. Successful EBPR relies on the growth of bacteria called polyphosphate-accumulating organisms (PAOs), which store phosphorus intracellularly as polyphosphate, thus removing it from wastewater. Metabolic models have been proposed which describe the measured chemical transformations, however genetic evidence is lacking to confirm these hypotheses. The aim of this research was to generate a metagenomic library from biomass enriched in PAOs as determined by phenotypic data and fluorescence in situ hybridisation (FISH) using probes specific for the only described PAO to date, Candidatus Accumulibacter phosphatis. DNA extraction methods were optimised and two fosmid libraries were constructed which contained 93 million base pairs of metagenomic data. Initial screening of the library for 16S rRNA genes revealed fosmids originating from a range of non-pure-cultured wastewater bacteria. The metagenomic libraries constructed will provide the ability to link phylogenetic and metabolic data for bacteria involved in nutrient removal from wastewater. Keywords DNA extraction; EBPR; metagenomic library; 16S rRNA gene.

Characterisation of red mud and seawater neutralised red mud using vibrational spectroscopic techniques

Bauxite refinery residues are derived from the Bayer process by the digestion of crushed bauxite in concentrated caustic at elevated temperatures. Chemically, it comprises, in varying amounts (depending upon the composition of the starting bauxite), oxides of iron and titanium, residual alumina, sodalite, silica, and minor quantities of other metal oxides. Bauxite residues are being neutralised by seawater in recent years to reduce the alkalinity in bauxite residue, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. A combination of X-ray diffraction (XRD) and vibrational spectroscopy techniques, including mid-infrared (IR), Raman, near-infrared (NIR), and UV-Visible, have been used to characterise bauxite residue and seawater neutralised bauxite residue. Both the ferrous (Fe2+) and ferric (Fe3+) ions within bauxite residue can be identified by their characteristic NIR bands, where ferrous ions produce a strong absorption band at around 9000 cm-1, while ferric ions produce two strong bands at 25000 and 14300 cm-1. The presence of adsorbed carbonate and hydroxide anions can be identified at around 5200 and 7000 cm-1, respectively, attributed to the 2nd overtone of the 1st fundamental overtones observed in the mid-IR spectra. The complex bands in the Raman and mid-IR spectra around 3500 cm-1 are assigned to the OH stretching vibrations of the various oxides present in bauxite residue, and water. The combination of carbonate and hydroxyl units and their fundamental overtones give rise to many of the features of the NIR spectra.

Interaction of aqueous inorganic orthophosphate and phosphate rock

An experimental study was made of the interaction of phosphate rock and aqueous inorganic orthophosphate, calcium, and hydroxyl ions. A model of the reaction was developed by observing electron diffraction patterns in conjunction with concentration changes of chemical components. The model was applied in explaining the performance of batch suspensions of powdered phosphate rock and packed columns of granular phosphate rock. In both cases the reaction consisted initially of a rapid nucleation phase that occurred in a time period of minutes. In the batch system the calcium phosphate nuclei then ripened into larger micro-crystals of hydroxyapatite, which eventually became indistinguishable from the original phosphate rock surface. During column operation the high supersaturation ratio that existed after the rapid nucleation phase resulted in a layer of small nuclei that covered a slowly growing hydroxyapatite crystal.

The column steady-state rate constant was found to increase with increasing temperature, pH, and fluoride concentration, and to decrease with increasing concentrations of magnesium sulfate, ammonium chloride, and bicarbonate ion.

An engineering feasibility study indicated that, based on economic considerations, nucleation of apatite on phosphate rock ore has a potential use as a wastewater phosphate removal treatment process.

Quantum Mechanics Studies of Fuel Cell Catalysts and Proton Conducting Ceramics with Validation by Experiment

We carried out quantum mechanics (QM) studies aimed at improving the performance of hydrogen fuel cells. This led to predictions of improved materials, some of which were subsequently validated with experiments by our collaborators.

In part I, the challenge was to find a replacement for the Pt cathode that would lead to improved performance for the Oxygen Reduction Reaction (ORR) while remaining stable under operational conditions and decreasing cost. Our design strategy was to find an alloy with composition Pt3M that would lead to surface segregation such that the top layer would be pure Pt, with the second and subsequent layers richer in M. Under operating conditions we expect the surface to have significant O and/or OH chemisorbed on the surface, and hence we searched for M that would remain segregated under these conditions. Using QM we examined surface segregation for 28 Pt₃M alloys, where M is a transition metal. We found that only Pt₃Os and Pt₃Ir showed significant surface segregation when O and OH are chemisorbed on the catalyst surfaces. This result indicates that Pt₃Os and Pt3Ir favor formation of a Pt-skin surface layer structure that would resist the acidic electrolyte corrosion during fuel cell operation environments. We chose to focus on Os because the phase diagram for Pt-Ir indicated that Pt-Ir could not form a homogeneous alloy at lower temperature. To determine the performance for ORR, we used QM to examine all intermediates, reaction pathways, and reaction barriers involved in the processes for which protons from the anode reactions react with O₂ to form H₂O. These QM calculations used our Poisson-Boltzmann implicit solvation model include the effects of the solvent (water with dielectric constant 78 with pH 7 at 298K). We found that the rate determination step (RDS) was the O_ad hydration reaction (O_ad + H₂O_ad -> OH_ad + OH_ad) in both cases, but that the barrier for pure Pt of 0.50 eV is reduced to 0.48 eV for Pt₃Os, which at 80 degrees C would increase the rate by 218%. We collaborated with the Pu-Wei Wu’s group to carry out experiments, where we found that the dealloying process-treated Pt2Os catalyst showed two-fold higher activity at 25 degrees C than pure Pt and that the alloy had 272% improved stability, validating our theoretical predictions.

We also carried out similar QM studies followed by experimental validation for the Os/Pt core-shell catalyst fabricated by the underpotential deposition (UPD) method. The QM results indicated that the RDS for ORR is a compromise between the OOH formation step (0.37 eV for Pt, 0.23 eV for Pt_2ML/Os core-shell) and H₂O formation steps (0.32 eV for Pt, 0.22 eV for Pt_2ML/Os core-shell). We found that Pt_2ML/Os has the highest activity (compared to pure Pt and to the Pt₃Os alloy) because the 0.37 eV barrier decreases to 0.23 eV. To understand what aspects of the core shell structure lead to this improved performance, we considered the effect on ORR of compressing the alloy slab to the dimensions of pure Pt. However this had little effect, with the same RDS barrier 0.37 eV. This shows that the ligand effect (the electronic structure modification resulting from the Os substrate) plays a more important role than the strain effect, and is responsible for the improved activity of the core- shell catalyst. Experimental materials characterization proves the core-shell feature of our catalyst. The electrochemical experiment for Pt_2ML/Os/C showed 3.5 to 5 times better ORR activity at 0.9V (vs. NHE) in 0.1M HClO₄ solution at 25 degrees C as compared to those of commercially available Pt/C. The excellent correlation between experimental half potential and the OH binding energies and RDS barriers validate the feasibility of predicting catalyst activity using QM calculation and a simple Langmuir–Hinshelwood model.

In part II, we used QM calculations to study methane stream reforming on a Ni-alloy catalyst surfaces for solid oxide fuel cell (SOFC) application. SOFC has wide fuel adaptability but the coking and sulfur poisoning will reduce its stability. Experimental results suggested that the Ni4Fe alloy improves both its activity and stability compared to pure Ni. To understand the atomistic origin of this, we carried out QM calculations on surface segregation and found that the most stable configuration for Ni₄Fe has a Fe atom distribution of (0%, 50%, 25%, 25%, 0%) starting at the bottom layer. We calculated that the binding of C atoms on the Ni4Fe surface is 142.9 Kcal/mol, which is about 10 Kcal/mol weaker compared to the pure Ni surface. This weaker C binding energy is expected to make coke formation less favorable, explaining why Ni₄Fe has better coking resistance. This result confirms the experimental observation. The reaction energy barriers for CHx decomposition and C binding on various alloy surface, Ni₄X (X=Fe, Co, Mn, and Mo), showed Ni₄Fe, Ni₄Co, and Fe₄Mn all have better coking resistance than pure Ni, but that only Ni₄Fe and Fe₄Mn have (slightly) improved activity compared to pure Ni.

In part III, we used QM to examine the proton transport in doped perovskite-ceramics. Here we used a 2x2x2 supercell of perovskite with composition Ba₈X₇M₁(OH)₁O₂₃ where X=Ce or Zr and M=Y, Gd, or Dy. Thus in each case a 4⁺ X is replace by a 3⁺ M plus a proton on one O. Here we predicted the barriers for proton diffusion allowing both includes intra-octahedron and inter-octahedra proton transfer. Without any restriction, we only observed the inter-octahedra proton transfer with similar energy barrier as previous computational work but 0.2 eV higher than experimental result for Y doped zirconate. For one restriction in our calculations is that the O_donor-O_acceptor atoms were kept at fixed distances, we found that the barrier difference between cerates/zirconates with various dopants are only 0.02~0.03 eV. To fully address performance one would need to examine proton transfer at grain boundaries, which will require larger scale ReaxFF reactive dynamics for systems with millions of atoms. The QM calculations used here will be used to train the ReaxFF force field.

Selective formation of aromatic amines by selenium-catalyzed reduction of aromatic nitro compounds with CO/H2O under atmospheric pressure

An efficient method for the catalytic reduction of aromatic nitro compounds to the corresponding aromatic amines is reported. In the presence of selenium as a catalyst, the aromatic nitro compounds are quantitively reduced by CO/H2O to form the corresponding amines under atmospheric pressure. The reduction occurs in high selectivity regardless of other reducible functionalities present on the aromatic ring. There exists a phase transfer process of the catalyst selenium in the reaction. (C) 2004 Elsevier B.V. All rights reserved.

拜耳法赤泥放射性特征及应用途径研究

赤泥是氧化铝生产过程中的工业固体废弃物,具有强碱性和高放射性两个特点。目前赤泥的处置方法主要是建设赤泥堆场，供长期堆放，尚没有对其进行大规模利用的成熟技术。 随着铝工业的发展，亟需开发赤泥处置与资源化利用的新工艺技术。本论文运用环境地球化学的理论方法，采用化学分析、选矿分离、放射性测试等技术手段，对贵州铝厂拜耳法赤泥的放射性特征进行了矿物学研究，并利用铁钛着色机理生产赤泥墙体装修材料进行了应用试验研究，指明了赤泥规模化综合利用的途径。 通过研究，得到以下主要结论： 1）初步确定了赤泥放射性元素主要来源于铝土矿原矿，并赋存于原矿残留的锆石和独居石中。 2) 贵州铝厂拜耳法赤泥所含放射性偏高，倘若利用赤泥制作建筑主体材料，需要慎重考虑。 3）探讨了不同选矿方法对赤泥放射性强度的变化情况，重选、磁选、加磁粉磁选所得赤泥组分与赤泥原样放射性相比较，没有显著性差异。采用现有选矿技术，难以达到分离富集赤泥中含放射性组分。 4）利用拜耳法赤泥中富含Fe2O3和TiO2的着色机理，加入一定量的页岩可以制得金红-褐色系列颜色的彩色墙体装修材料。采用现有烧结砖厂一般生产工艺，利用拜耳法赤泥生产烧结制品，是规模化处理赤泥的一条可行途径。 本论文的研究结果指明了赤泥可行的利用途径是用于建材领域，为制定赤泥大规模资源化利用的技术路线提供了一定的理论基础。

Combined single-pass conversion of methane via oxidative coupling and dehydro-aromatization

A single-pass process with the combination of oxidative coupling (OCM) and dehydro-aromatization (MDA) for the direct conversion of methane is carried out. With the assistance of the OCM reaction over the SrO-La2O3/CaO catalyst loaded on top of the catalyst bed, the duration of the dehydro-aromatization reaction catalyzed by a 6Mo/HMCM-49 catalyst shows a significant improvement, and. the initial deactivation rate constant of the overall process revealed about 1.5 x 10(-6) s(-1). Up to 72 h on stream, the yield of aromatics was still maintained at 5.0% with a methane conversion of 9.6%, which is obviously higher than that reported for the conventional MDA process with single catalyst. Upon the TPR results, this wonderful enhancement would be attributed to an in-situ formation of CO2 and H2O through the OCM reaction, which serves as a scavenger for actively removing the coke formed during the MDA reaction via a reverse Boudouard reaction and the water gas reaction as well.

Desarrollo de catalizadores en sistemas de reacción avanzados para la producción de hidrógeno a partir de biogás

[ES]En el presente documento se expone el estudio experimental que consiste en la comparación de diferentes catalizadores en sistemas de reacción avanzados, microrreactores, para la producción de hidrógeno a partir de biogás. El hidrógeno es un vector energético que puede emplearse como combustible, y por tanto, un candidato perfecto para sustituir aquellos combustibles provenientes de fuentes fósiles. Este Proyecto de Fin de Grado se ha basado en desarrollar el proceso conocido como tri-reformado de biogás. Esta técnica, al contrario que las técnicas convencionales de producción, presenta numerosas ventajas ya que la materia prima empleada, el biogás, es una fuente de origen renovable. Para llevar a cabo este estudio se han preparado distintos catalizadores, basados todos ellos en platino. La elección de este metal noble es debido a su alto grado de reactividad, especialmente en sistemas de reacción micro-estructurados. Con el objetivo de reducir los costes asociados al propio catalizador, se añadieron, junto con el platino, otros metales más baratos a fin de analizar su idoneidad en el proceso del tri-reformado. Por tanto, partiendo de un catalizador de referencia que contiene un 5% de platino, se prepararon otros catalizadores mantenido constante, en un 5%, la composición de metal total. Estos catalizadores se han denominado de la siguiente manera: 2.5(Pt-Me), siendo Me cada especie metálica diferente. Tras preparar los catalizadores, se llevaron a cabo diferentes experimentos con un reactor convencional de lecho fijo. El objetivo fue establecer unas condiciones de operación tal que asegurasen una adecuada comparación entre catalizadores. De este modo, se realizaron ensayos de actividad catalítica a diferentes temperaturas y velocidades espaciales para someter a los catalizadores a condiciones de operación extremas, bajo las cuales, las diferencias entre catalizadores fueran más notorias. Una vez detalladas las condiciones de operación adecuadas para la comparación de catalizadores, se llevaron a cabo los correspondientes ensayos con los catalizadores impregnados en los sistemas de reacción avanzados, denominados micorreactores. Estos ensayos se basaron en operar a una velocidad espacial constante para estudiar la influencia de la temperatura. Además, se llevaron a cabo ensayos de estabilidad de hasta 110 horas en las condiciones de operación más desfavorables. Por último se compararon las conversiones de CH4 y CO2 y el rendimiento de H2 de todas las formulaciones catalíticas preparadas, y se concluyó que el mejor candidato para el proceso del tri-reformado es el catalizador 2.5(Pt-Pd).

Utilização de lama vermelha para oxidação eletrolítica assistida por plasma de liga de alumínio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)