Rota hidrometalúrgica de recuperação de molibdênio, cobalto, níquel e alumínio de catalisadores gastos de hidrotratamento em meio ácido

This work describes a hydrometallurgical route for processing spent commercial catalysts (CoMo and NiMo/Al2O3). Samples were preoxidized (500 ºC, 5 h) in order to eliminate coke and other volatile species present. The calcined solid was dissolved in concentrated H2SO4 and water (1:1 vol/vol) at 90 ºC; the insoluble matter was separated from the solution. Molybdenum was recovered by solvent extraction using tertiary amines at pH around 1.8. Cobalt (or nickel) was separated by addition of aqueous ammonium oxalate at the above pH. Phosphorus was removed by passing the liquid through a strong anion exchange column. Aluminum was recovered by neutralizing the solution with NaOH. The route presented in this work generates less final aqueous wastes because it is not necessary to use alkaline medium during the metal recovery steps.

Treatment of oily wastewater by ultrafiltration: The effect of different operating and solution conditions

In many industries, such as petroleum production, and the petrochemical, metal, food and cosmetics industries, wastewaters containing an emulsion of oil in water are often produced. The emulsions consist of water (up to 90%), oils (mineral, animal, vegetable and synthetic), surfactants and other contaminates. In view of its toxic nature and its deleterious effects on the surrounding environment (soil, water) such wastewater needs to be treated before release into natural water ways. Membrane-based processes have successfully been applied in industrial applications and are considered as possible candidates for the treatment of oily wastewaters. Easy operation, lower cost, and in some cases, the ability to reduce contaminants below existing pollution limits are the main advantages of these systems. The main drawback of membranes is flux decline due tofouling and concentration polarisation. The complexity of oil-containing systems demands complementary studies on issues related to the mitigation of fouling and concentration polarisation in membranebased ultrafiltration. In this thesis the effect of different operating conditions (factors) on ultrafiltration of oily water is studied. Important factors are normally correlated and, therefore, their effect should be studied simultaneously. This work uses a novel approach to study different operating conditions, like pressure, flow velocity, and temperature, and solution properties, like oil concentration (cutting oil, diesel, kerosene), pH, and salt concentration (CaCl2 and NaCl)) in the ultrafiltration of oily water, simultaneously and in a systematic way using an experimental design approach. A hypothesis is developed to describe the interaction between the oil drops, salt and the membrane surface. The optimum conditions for ultrafiltration and the contribution of each factor in the ultrafiltration of oily water are evaluated. It is found that the effect on permeate flux of the various factors studied strongly depended on the type of oil, the type of membrane and the amount of salts. The thesis demonstrates that a system containing oil is very complex, and that fouling and flux decline can be observed even at very low pressures. This means that only the weak form of the critical flux exists for such systems. The cleaning of the fouled membranes and the influence of different parameters (flow velocity, temperature, time, pressure, and chemical concentration (SDS, NaOH)) were evaluated in this study. It was observed that fouling, and consequently cleaning, behaved differently for the studied membranes. Of the membranes studied, the membrane with the lowest propensity for fouling and the most easily cleaned was the regenerated cellulose membrane (C100H). In order to get more information about the interaction between the membrane and the components of the emulsion, a streaming potential study was performed on the membrane. The experiments were carried out at different pH and oil concentration. It was seen that oily water changed the surface charge of the membrane significantly. The surface charge and the streaming potential during different stages of filtration were measured and analysed being a new method for fouling of oil in this thesis. The surface charge varied in different stages of filtration. It was found that the surface charge of a cleaned membrane was not the same as initially; however, the permeability was equal to that of a virgin membrane. The effect of filtration mode was studied by performing the filtration in both cross-flow and deadend mode. The effect of salt on performance was considered in both studies. It was found that salt decreased the permeate flux even at low concentration. To test the effect of hydrophilicity change, the commercial membranes used in this thesis were modified by grafting (PNIPAAm) on their surfaces. A new technique (corona treatment) was used for this modification. The effect of modification on permeate flux and retention was evaluated. The modified membranes changed their pore size around 33oC resulting in different retention and permeability. The obtained results in this thesis can be applied to optimise the operation of a membrane plant under normal or shock conditions or to modify the process such that it becomes more efficient or effective.

Evaluation of sample processing methods for the polar contaminant analysis of sewage sludge using liquid chromatography - mass spectrometry (LC/MS)

Monitoring of sewage sludge has proved the presence of many polar anthropogenic pollutants since LC/MS techniques came into routine use. While advanced techniques may improve characterizations, flawed sample processing procedures, however, may disturb or disguise the presence and fate of many target compounds present in this type of complex matrix before analytical process starts. Freeze-drying or oven-drying, in combination with centrifugation or filtration as sample processing techniques were performed followed by visual pattern recognition of target compounds for assessment of pretreatment processes. The results shown that oven-drying affected the sludge characterization, while freeze-drying led to less analytical misinterpretations.

Investigating the spontaneous formation of SDS micelle in aqueous solution using a coarse-grained force field

A 1µs Molecular Dynamic simulation was performed with a realistic model system of Sodium Dodecyl Sulfate (SDS) micelles in aqueous solution, comprising of 360 DS-, 360 Na+ and 90000 water particles. After 300 ns three different micellar shapes and sizes 41, 68 and 95 monomers, were observed. The process led to stabilization in the total number of SDS clusters and an increase in the micellar radius to 2.23 nm, in agreement with experimental results. An important conclusion, is be aware that simulations employed in one aggregate, should be considered as a constraint. Size and shape distribution must be analyzed.

Solution thermodynamics of methocarbamol in some ethanol + water mixtures

Apparent thermodynamic functions, Gibbs energy, enthalpy and entropy of solution and mixing, for methocarbamol in ethanol + water mixtures, were evaluated from solubility data determined at temperatures from 293.15 K to 313.15 K and from calorimetric values of drug fusion. The drug solubility was greatest in the mixtures with 0.70 or 0.80 mass fraction of ethanol and lowest in neat water across all temperatures studied. Non-linear enthalpy-entropy compensation was found for the dissolution processes. Accordingly, solution enthalpy drives the respective processes in almost all the solvent systems analyzed.

Processing of spent NiW/Al2O3 catalysts

Spent oxidized (500 ºC, 5 h) commercial NiW/Al2O3 catalysts were processed using two different routes: a) fusion with NaOH (650 ºC, 1 h), the roasted mass was leached in water; b) leaching with HCl or H2SO4 (70 ºC, 1-3 h). HCl was the best leachant. In both routes, soluble tungsten was extracted at pH 1 with Alamine 336 (10 vol.% in kerosene) and stripped with 2 mol L-1 NH4OH (25 ºC, one stage, aqueous/organic ratio = 1 v/v). Tungsten was isolated as ammonium paratungstate at very high yield (> 97.5%). The elements were better separated using the acidic route.

Equilibrium studies of 2,2'-(5-bromo-6-methylpyrimidine-2,4-diyl)bis(azanediyl)dipropanoic acid with some transition-metal ions in aqueous solution

The stability constants of the 1:1 complexes formed between M2+ (M2+: Mn2+, Ni2+, Cu2+, or Cd2+) and BMADA2- (BMADA: 2,2'-(5-bromo-6-methylpyrimidine-2,4 diyl)bis(azanediyl)dipropanoic acid) were determined by potentiometric pH titration in aqueous solution (I = 0.1 mol L-1, NaNO3, 25 °C). The stability of the binary M - BMADA complexes is determined by the basicity of the carboxyl or amino groups. All the stability constants reported in this work exhibit the usual trend, and the order obtained was Mn2+< Ni2+ < Cu2+ > Cd2+. The observed stability order for BMADA approximately follows the Irving - Williams sequence. In the M - BMADA complexes, the M ion is able to form a macrochelate via the pyrimidine group of BMADA.

Determination of Mn2+ ion by solution scanometry as a new, simple and inexpensive method

In this research, scanometry was used as a new, simple, fast and inexpensive method for a colorimetric determination of Mn2+ ion in water samples and thermocouple wire through the use of periodate reagent in an acidic medium. The results showed the oxidization of colorless Mn2+ ion by periodate and the formation of a purplish MnO4- ion. The system had a linear range of 1.0 to 70.0 µg mL-1 Mn2+ ion with a detection limit of 0.314 µg mL-1 and a relative standard deviation of 2.77% for G color value. This method has the capability to determine low levels of Mn2+ ion in thermocouple wire and water samples.

Seurantakomponentin kehitys tapahtumankäsittelyjärjestelmään

Tapahtumat ovat perusta monille nykyaikaisille tietoteknisille palveluille. Yksittäinen tapahtuma voidaan nähdä työtehtävänä, joka käsittelevän järjestelmän tulee suorittaa. Tapahtumankäsittely pyrkii pitämään järjestelmän tunnetussa ja ristiriidattomassa tilassa. Tämä toteutetaan pitämällä huolta, että jokainen tapahtuma joko onnistuu tai epäonnistuu kokonaisuudessaan. Tapahtumankäsittelyjärjestelmät ovat kasvaneet ja yhtäaikaisten käsiteltävien tapahtumien määrä noussut palveluiden siirtyessä yhä enemmän tietoverkkoihin. Samalla järjestelmien kehittäminen ja ylläpito vaikeutuvat, jolloin kehittäjät tarvitsevat parempia työkaluja järjestelmän valvontaan. Tapahtumankäsittelyn seuranta pyrkii seuraamaan järjestelmän sisäistä toimintaa yksittäisen tapahtuman tai osatapahtuman tarkkuudella. Riippuen toteutuksesta kehittäjä voi joko tarkkailla järjestelmää reaaliaikaisesti tai jälkikäteen suorituksen perusteella tallennetun seurantatiedon avulla. Työssä esitellään tapahtumanseurantakomponentin suunnitteluprosessi ratkaisuineen, joka mahdollistaa tapahtumien suorituksen tarkkailun, seurantatiedon tallentamisen sekä tulosten tarkastelun jälkikäteen. Työ on toteutettu osaksi Syncron Tech Oy:n Syncware-ohjelmistoalustaa.

Liikkuvan kenttätyön hallinta etätunnistusta ja paikannusta hyödyntävällä mobiilijärjestelmällä

Liikkuvan kenttätyön työntekijät suorittavat työpäivän aikana työtä useassa eri työkohteessa. Työkohteilla suoritettujen työtehtävien kirjaus tapahtuu usein jälkikäteen ja muistinvaraisesti. Diplomityön tavoitteena on esittää ratkaisu liikkuvan kenttätyön työkirjausten automatisointiin. Tavoitteen mukaisen etätunnistusta ja paikannusta hyödyntävän mobiilijärjestelmän avulla työntekijöiden käsinkirjoitetut ja mahdollisesti puutteelliset työkirjaukset korvataan automaattisilla ja täsmällisillä kirjauksilla. Järjestelmän tavoitteena on vähentää työntekijöiden työkuormaa. Työssä arvioidaan etätunnistuksen hyödyntämistä mobiilisovelluksen käyttöä helpottavana tekniikkana. Parhaimmillaan etätunnistus poistaa kokonaan mobiililaitteen näppäilytarpeen, mutta aiheuttaa osaltaan lisää työtä järjestelmän ylläpitoon. Työn tuloksissa esitetään myös satelliittipaikannuksen todettu tarkkuus ja soveltuvuus liikkuvan kenttätyön tarpeisiin taajama- ja kaupunkialueella. Varsinkin kaupunkialueella satelliittiperustaisen paikkatiedon tehokas hyödyntäminen edellyttää suodatusta ja älykkyyttä paikkatiedon prosessointiin.

Data Consistency by a Metadata Management Solution

This thesis consists of three main theoretical themes: quality of data, success of information systems, and metadata in data warehousing. Loosely defined, metadata is descriptive data about data, and, in this thesis, master data means reference data about customers, products etc. The objective of the thesis is to contribute to an implementation of a metadata management solution for an industrial enterprise. The metadata system incorporates a repository, integration, delivery and access tools, as well as semantic rules and procedures for master data maintenance. It targets to improve maintenance processes and quality of hierarchical master data in the case company’s informational systems. That should bring benefits to whole organization in improved information quality, especially in cross-system data consistency, and in more efficient and effective data management processes. As the result of this thesis, the requirements for the metadata management solution in case were compiled, and the success of the new information system and the implementation project was evaluated.

Customer knowledge processing in key account management

The ability of the supplier firm to generate and utilise customer-specific knowledge has attracted increasing attention in the academic literature during the last decade. It has been argued the customer knowledge should treated as a strategic asset the same as any other intangible assets. Yet, at the same time it has been shown that the management of customer-specific knowledge is challenging in practice, and that many firms are better at acquiring customer knowledge than at making use of it. This study examines customer knowledge processing in the context of key account management in large industrial firms. This focus was chosen because key accounts are demanding and complex. It is not unusual for a single key account relationship to constitute a complex web of relationships between the supplier and the key account – thus easily leading to the dispersion of customer-specific knowledge in the supplier firm. Although the importance of customer-specific knowledge generation has been widely acknowledged in the literature, surprisingly little attention has been paid to the processes through which firms generate, disseminate and use such knowledge internally for enhancing the relationships with their major, strategically important key account customers. This thesis consists of two parts. The first part comprises a theoretical overview and draws together the main findings of the study, whereas the second part consists of five complementary empirical research papers based on survey data gathered from large industrial firms in Finland. The findings suggest that the management of customer knowledge generated about and form key accounts is a three-dimensional process consisting of acquisition, dissemination and utilization. It could be concluded from the results that customer-specific knowledge is a strategic asset because the supplier’s customer knowledge processing activities have a positive effect on supplier’s key account performance. Moreover, in examining the determinants of each phase separately the study identifies a number of intra-organisational factors that facilitate the process in supplier firms. The main contribution of the thesis lies in linking the concept of customer knowledge processing to the previous literature on key account management. Moreover, given than this literature is mainly conceptual or case-based, a further contribution is to examine its consequences and determinants based on quantitative empirical data.