Academic literature on the topic 'Aluminum hydrolysis'

A range extender in a battery electric vehicle supplements the existing drive system as an add-on module. Range extenders can comprise of any combination of conventional fuel, battery or fuel cell driven modules. The idea of a sub-system changes with the type of range extender. In this work, hydrogen generation is studied, a fuel is used to power the range extender via a fuel cell.The thesis presents the work in progress for development of the sub-system for a range extender based on on-board production of hydrogen for automobiles. Several aspects of chemistry play equally pivotal role in control, hassle-free operation and safety of the system. Aftertreatment of the fuel by-products is the notorious issue that limits the reusing the reactor effecting the range extender. Along with this, reducing the reaction time with minimal usage of fuel is investigated. Both of these pressing issues are resolved correspondingly to an extent with the addition of several chemicals. In addition, with the help of characterization techniques, a robust circular economy outlook of the range extender system has been initiated.<br>En distansförlängare i ett eldrivet fordon kompletterar det befintliga drivsystemet som en tilläggsmodul. Distansförlängaren kan vara olika kombinationer av konventionella bränsle-, batteri- och bränslecelldrivna moduler. Utformningen av de övriga delarna av undersystemet beror på vilken distansförlängare som används. I detta arbete drivs distansförlängaren av en bränslecell, bränslet till bränslecellen genereras i distansförlängaren. Avhandlingen presenterar det pågående arbetet för utvecklingen av undersystemet hos en distansförlängare. Undersystemet baseras på ombordsproduktion av väte för bilar. Flera aspekter av kemi spelar en lika viktig roll i kontroll, problemfri drift och säkerhet. Efterbehandling av bränslets biprodukter är det ständiga problemet som begränsar reaktorns återanvändbarhet vilket påverkar distansförlängaren. Tillsammans med detta undersöks minskning av reaktionstiden med minimal användning av bränsle. Båda dessa pressande problem löses i en utsträckning med tillsatsen av flera kemikalier. Dessutom har en robust cirkulärekonomisk syn på distansförlängaren utvecklats med hjälp av olika karakteriseringstekniker.

Abstract This thesis focuses on the molecular-level chemistry of the solvation of aluminum salts. Fundamental aspects such as, structural characteristics of the aluminum molecules, hydrolysis, acidity, solvation structure, effect of counter ions, and chemical stability are discussed herein. Static computations augmented with the conductor-like screening model (COSMO) were used to investigate hundreds of planar and cyclic configurations of dimeric, trimeric, tetrameric, and pentameric aluminum complexes. Car–Parrinello molecular dynamics (CPMD) calculations were used to expand investigations to aqueous environments. This thesis consists of four articles and one additional article. The first paper focuses on the structural analysis of the hydrolysis products of AlCl3 · 6H2O. Dimeric, trimeric, and tetrameric aluminum (chloro)hydroxides were investigated in both gas and liquid phase. The liquid environment was modeled by using COSMO. The second and the additional paper concentrate on the chemistry of aluminum sulfate complexes. The second article focuses on identifying hydrolysis products of AlCl3 · 6H2O in the presence of sulfate (H2SO4). The additional paper focuses on the structural characteristics of the hydrolysis products of Al2 (SO4)3 · 18H2O. Structural information was deduced from the ESI MS results with the aid of computational methods. Detected cationic structures closely resembled the aluminum chlorohydrate analogues introduced in the first paper. The third and fourth articles are devoted to the hydrolysis, stability, and dynamics of dimeric and pentameric aluminum (chloro)hydroxides in aquatic environments. During the CPMD simulations, several spontaneous associative hydration reactions were detected in the primary hydration shell of the complexes. Dimeric aluminum chlorohydrates were detected to be stable in liquid conditions, whereas the pentameric aluminum complexes experienced significant topological changes during the simulations. Constrained simulations were used to reveal the role of chloride ions in the hydrolysis processes of dimeric complexes. The effect of the empirical van der Waals corrections to the dynamics of the simulations was also tested for the pentameric system. The results of this thesis showed unequivocally that computational chemistry provides effective tools for structural analysis of inorganic complexes such as, aluminum chlorohydrates and sulfates in both gas and liquid phase. In addition, calculations provided answers to the anomalies detected in the experiments. Hence, theoretical methods are highly recommended to be used alongside with conventional experimental methods in the interpretation of the aluminum species in aqueous solutions and to widen the overall chemical perspective of the hydrolysis of aluminum salts.

The nature of chemical reactions taking place during the titration of dilute Al solutions in the presence of either chloride or sulfate were examined by refining the apparent Al hydrolysis products assuming the presence of solution species with n (OH/Al mole ratio) equal to 1, 2, 2.5, 3 and 4. The second and third hydrolysis products for Al were refined by comparison of calculated titration patterns to those observed for 10⁻³, 10⁻⁴ and 10⁻⁵ M Al in 1 M, 0.1 M and 0.01 M KCl. A large degree of polynuclear character of Al solutions was found even at Al concentrations as low as 10⁻⁵ M. The n value and size of the polynuclear complexes are affected by Al concentration. The concentration constant, pQ₁₃ is found to be at least 17.4-17.7. It is concluded that the mononuclear Al(OH)₂ species is never significant. Use of statistical analysis of the data and graphical methods did not result in consistent data for polymer size determinations. The lower pQ values for mononuclear Al hydrolysis are explained by the structural instability of the mononuclear complexes. The bond strengths required for the bonds in the second and third hydrolysis complexes are often larger than those allowed for octahedral coordination. For that reason, the pQ values would be lower than calculated by extrapolation between the stable first and fourth hydrolysis constants. A new polynuclear complexation mechanism for Al is proposed to account for the high concentration of high n value polynuclear species in the titration refinements. The proposed linear l double chain structure has a structure consistent with boehmite and diaspore. This structure differs from the linear single chain and ring based polynuclear structures by the presence of rows of three coordinated oxygens in the bond central chain and rows of two and one coordinated oxygens along the plane edges. A rearrangement of internal charge in this structure is proposed in which part of the charge is removed from the three coordinated oxygens to result in an uncharged hydroxyl with the charge shifted to the one coordinated site neutralizing the hydroxyl. This results in a general formula for the polynuclear structure of (Al(OH)₃)_x(Al(OH)₂)₂²⁺. This structure results in a higher n value for a lower number of Al than does the other polynuclear complexation schemes and therefore explains the presence of high n value polymers in unaged Al solutions which would have required polymers of greater than a hundred Al cations. The observed presence of a second Al plateau on titration patterns with Al concentrations greater than 5 x10⁻⁵ M could not be the result of the onset of precipitation as earlier proposed. It is proposed that at a pH in the 6 to 7 range, a change of some of the one coordinated sites on the edge of the larger polynuclear and precipitant structures from water to hydroxyls results in a change in net edge charge from net positive to net negative which causes an increased rate of crystal growth due to the unlike charge between the edges and the smaller polynuclear and mononuclear complexes. The refinement of Al titration data in K₂SO₄, provide pQ values one to three pQ units lower than those obtained from equivalent KCl solutions. A catalytic mechanism is proposed in which Al polymerization is facilitated by the formation of mononuclear Al hydroxy sulfate complexes which combine together to form nonsulfate containing polynuclear complexes. The increased hydrolyzed concentration and lower ionic charge resulting from these complexes would increase the rate of polymerization in these systems. Evidence for the presence of mononuclear hydroxy sulfate complexes comes from the better fit for titration patterns in sulfate systems which would not have been observed for increased polymerization alone.<br>Ph. D.

Hydrolysis products of aluminum that exist in aqueous solutions play an important role in controlling the fate and transport of contaminants and are also used for coagulants to purification of wastewater streams. Adsorption of contaminants such as heavy metals and organics are widely recognized, but the molecular level understanding of the mechanism of action has not been clearly defined. In this research we present the crystallization, structural characterization and chemical characterization of three novel Keggin-type aluminum polycations including ((Al(IDA)H2O)2(Al30O8(OH)60(H2O)22)(2,6 NDS)4(SO4)2Cl4(H2O)40) (Al32-IDA),[(Cu(H2O)2(µ2-OH)2)2(Al2(µ4-O)8(Al28(µ2-OH)50(µ3-OH)6(H2O)26(2,6-NDS)9(H2O)52]-(CuAl30) and [(Zn(NTA)H2O)2(Al(NTA)(µ2-OH)2)2(Al30(µ2-OH)54(µ3-OH)6(µ4-O)8(H2O)20(2,6-NDS)5(H2O)64]-(ZnAl32) where IDA = iminodiacetic acid, NTA- Nitrilotriacetic acid, and 2,6 NDS = 2,6 napthalene disulfonate. These compounds are the first ever reported Keggin-type aluminum species that have been functionalized with organics and heavy metal cations. Structural characterization of these compounds was done by means of single crystal X-ray diffraction along with FTIR, TGA, SEM/EDS and PXRD techniques for chemical characterization. This study provides more insight into the coagulation process and can be employed in developing optimized coagulants for enhanced water purification.

To offer better solutions for the recycling of salt cake from secondary aluminum melting, several innovative investigations were carried out based on hydrometallurgical and pyrometallurgical views. Thermal diffusivity measurements as a function of temperature on salts-Al composites having various compositions (0, 2, 4, 6, 8, 10, 12wt pct metallic Al) were carried out. Its attempt to derive theoretical relationships between aluminium contents in the salt-Al composites and the thermal conductivities so that these would serve as calibration curves for industrial samples taken out from secondary aluminium re-melting at a later stage. The AlN hydrolysis behavior in NaCl solution was investigated by immersing pure AlN powder in deionized water, 0.3mol/l NaCl aq, 0.6mol/l NaCl aq and NaCl solution respectively with CO2 bubbling at 291K. The results showed that AlN powder underwent enhanced hydrolysis in NaCl aq than that in deionized water, while, the introduction of CO2 was found to hinder the hydrolysis even in the presence of NaCl. The characterization of the products after hydrolysis was carried out using XRD, SEM and TEM analyses. It was shown that the hydrolysis process included a slow-reaction period involving the dissolution of aluminum hydroxide layer around raw AlN particle, followed by the precipitation of aluminum hydroxide gel and the crystallization of boehmite, bayerite and gibbsite. The effects of sodium chloride concentration on the hydrolysis behavior are presented. The leaching process in CO2-saturated water showed that, at a solid to liquid ratio of 1:20 and 3h at 291K, the extraction of Na and K from the dross could be kept as high as 95.6% and 95.9%, respectively. At the same time, with continuous CO2 bubbling, the mass of generated NH3 during the leaching process decreased significantly, also the escaping NH3 gas decreased from 0.25mg in pure water down to &lt;0.006mg. The above results showed that the introduction of CO2 causes hindrance to the hydrolysis of AlN, meanwhile, effective absorption of ammonia. The plausible mechanisms for the observed phenomena are discussed. The concept of the leaching of the salt cake by carbonated water and the consequent retention of AlN in the leach residue opens up a promising route towards an environment-friendly recycling process for the salt cake viz. recovery of the salts, utilization of CO2 and further processing of the dross residue, towards the synthesis of SiAlON from the leach residues.   In alternative route to the processing of salt cake, the ammonia gas evolved by hydrolysis of AlN was collected by CO2-saturated water during water leaching at 373K. The products, i.e. ammonium carbonates which are free of chlorides, has application as a fertilizer, besides that, this method also has the advantage of fixing carbon from CO2, which is the subject of many investigations around the world. The oxidation behavior of composites SiMgAlON phases (β-SiAlON, MgAlON and 15R) synthesized from the residue during the leaching treatment of salt cake and corresponding synthetic samples was investigated in air by thermogravimetric measurements. The oxidation studies reveal the effects of impurities, namely, Fe2O3 and CaO present in the salt cake residue. From the view of kinetics, the addition of Fe2O3 brings a lower activation energy and more aggressive oxidation. The additive of CaO caused the shrinkage during the synthesis and liquid formation during the oxidation above 1673K, thus retard the oxidation rate. The impurities of CaO and Fe2O3 in the leaching residue can result in an aggressive oxidation at low temperature and a protective oxidation at temperatures above the eutectic point. From the view of phase evolution, with the progress of oxidation, the composition of the material being oxidized moved towards the Al2O3-rich corner of MgO-Al2O3-SiO2 or CaO-MgO-Al2O3-SiO2 phase diagrams relevant to SiMgAlON composite. At lower temperatures, the addition of Fe2O3 and CaO facilitated the formation of cordierite and anorthite, respectively. With the increasing of temperature, islands of silicate melt were formed dissolving these oxides, with the liquidus temperature getting lowered as a consequence. The liquid phase formed engulfed the adjacent solid phases providing strong mobility for the cations and enabling the crystal growth. As a result, intermediate products, i.e. cordierite, anorthite, spinel, which formed earlier during oxidation are found to get dissolved in the liquid phase.<br><p>QC 20120912</p>

Les acides organiques modifient considérablement le déroulement de l'hydrolyse de l'aluminium par blocage des oligomères intermédiaires entre le monomère et le tridecamère. Les précipités présentent une structure variable suivant l'échelle d'observation

Abstract This thesis is focused on the hydrolysis of aluminium, the polymerisation of the hydrolysis products, and how these can be monitored by mass spectrometric methods. The main aim of this research is to figure out how the aqueous speciation of aluminium changes as a function of pH (3.2–10), concentration (1–100 mM), reaction time (1s–14d), and counter anion (Cl-, SO42-, HCOO-). The method used was electrospray mass spectrometry. The results showed more variable speciation than those suggested earlier. The main species were Al2, Al3, and Al13, which were found in all of the conditions under scrutiny. The effect of pH was the most remarkable of all the parameters researched. The formation of large highly charged complexes was strongly dependent on it. Also the Al-concentration in the bulk solution had a clear effect on speciation: in dilute solutions there were more protonated ligands and less attached counter anions. This could mean that the species in more diluted bulk solutions had fewer different states of charge. Reaction time caused only minor changes to speciation in the initial pH: there was slightly more variation of a certain sized species in the aged solution. In elevated pH, the birth of important Al13 oligomers was time dependent. The effect of the counter anion was tremendous. In a chloride environment the speciation was rich and diversified. With sulphate the speciation was limited to solid- like compounds, and the variation of single-sized species was almost lacking. The formate as a counter anion caused most surprising results; the charge of aluminium in some studied complexes was lowered from the common 3+ to 1+. If this reaction also occurs in natural circumstances, the uses of aluminium formate would be wide. The results can be utilised in following the progress of dissolution, the mobilization and toxicity of aluminium in natural waters, as well as in water purification, and in reaching minimal chemical contamination levels in sludge as well as in aqueous waste.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)<br>Levando em consideração medidas para diminuir os efeitos das mudanças climáticas e tecnologias que auxiliam na segurança energética, esta dissertação tem como tema central o estudo da geração de gás hidrogênio como energia alternativa. O gás hidrogênio é um vetor energético com reduzidas emissões de poluentes na atmosfera se comparados com as fontes tradicionais existentes de energia. No entanto, estudos e pesquisas sobre suas potencialidades e viabilidades, tanto técnicas quanto socioeconômicas e ambientais, precisam ser desenvolvidas para amadurecimento tecnológico. O objetivo desta dissertação é analisar a produção de hidrogênio por hidrólise alcalina, com a reutilização de alumínio, correlacionando-a aos aspectos da sustentabilidade. Parte-se de um processo já conhecido e bem difundido no meio científico o qual será analisado e discutido suas possibilidades como tecnologia alternativa para produção de energia. O método empregado para a análise foi bibliográfico junto com o levantamento de dados primários em laboratório de um processo com requerimento de patente, dando caráter de pesquisa exploratória e descritiva. Os principais resultados técnicos foram: vazão média 77,53 ml.(min.g) -1 de H2, com pureza de 84,20%. Em seguida, realizou-se uma análise econômica, em moeda nacional, real R$/(m³.H2) e dólar norte-americano US$/kWh, comparando com outros estudos que determinaram o custo de produção em processos de geração deste tipo do gás. Estruturou-se uma matriz de aspectos e impactos que ilustram os potenciais efeitos na geração de energia. Concluiu-se que à geração de gás hidrogênio por hidrólise alcalina com a reutilização de alumínio secundário contribui para a visão direcionada para a sustentabilidade do planeta, podendo ser uma alternativa energética descentralizada.<br>Taking into account measures to reduce the effects of climate change and technologies that help energy security, this dissertation focuses on the study of generation of hydrogen gas as alternative energy. Hydrogen gas is an energy vector with reduced emissions of pollutants into the atmosphere compared to existing traditional sources of energy. However, studies and research on their potentialities and viabilities, both technical and socioeconomic and environmental, need to be developed for technological maturation. The objective of this dissertation is to analyze the production of hydrogen by alkaline hydrolysis, with the reuse of aluminum, correlating it to the aspects of sustainability. It starts from a process already known and well diffused in the scientific environment which will be analyzed and discussed its possibilities as alternative technology for energy production. The method used for the analysis was bibliographic along with the collection of primary data in the laboratory of a process with patent application, giving character of exploratory and descriptive research. The main technical results were: average flow 77.53 ml (min.g) -1 .H2, with a purity of 84.20%. Then, an economic analysis was performed in national currency, real R $ / (m³.H2) and US$ / kWh, comparing with other studies that determined the cost of production in this type of generation processes. gas. A matrix of aspects and impacts was drawn up illustrating the potential effects on energy generation. It was concluded that the generation of hydrogen gas by alkaline hydrolysis with the reuse of secondary aluminum contributes to the vision aimed at the sustainability of the planet, and can be a decentralized energy alternative.

La thermohydrolyyse, obention d'une phase solide par ebullition prolongee d'une solution initialement homogene, peut etre une technique interessante. Elle assure une bonne reproductibilite et limite la dispersion des proprietes texturales des solides obtenus. Des hydroxysulfates appartenant a la famille des alunites peuvent se former par thermohydrolyse de solutions de sulfate d'aluminium. L'influence de la composition des solutions a ete etudiee. Il est clairement etabli que l'alunite se forme en presence des cations na#+ ou nh#4#+ mais non pas en presence de li#+. Le rendement de precipitation croit lorsque les rapports so#4#2#-/al#3#+ avec (na#+ -o) et na#+ (ounh#4#+)al#3#+ augmentent. Une diminution rapide du ph apparait en meme temps que la temperature augmente: a l'ebullition le ph se stabilise pendant toute la duree de l'hydrolyse. L'utilisation des constantes d'hydrolyse et de complexation generalement admises, l'exploitation des spectres de la rnn de #2#7 al qui montrent le role du complexe al(h#2o)#5so#4#+, ont conduit a proposer un mecanisme dans lequel se forme d'abord l'anion al#3(h#2o)#8(os)#6(so#4)#2#-. Ensuite il se deshydrate et precipite avec l'alcalin, si ce dernier est suffisamment volumineux. La composition des solides obtenus depend etroitement de celle de la solution mere, la variation des parametres cristallins peut etre directement lies a la concentration des ions sodium de la solution. Par pyrolyse a l'air a environ 900c, les alubates conduisent a l'oxyde d'aluminium, al#2o#3 pour la natroalunite et al#2o#3 pour l'ammonialunite. La precipitation simultanee des ions mg#2s+ et al#3#+ par cette technique conduit a ph 12, a l'hydroxyde double mg#4al#2(08)#1#4, 3h#2o. Les conditions de synthese tres dures entrainent la formation de phases parasites. La modification du rapport al#3/mgh#2#+ entre 0,5 et 0,8