The Influence of Process Conditions on the Deresination Efficiency in Mechanical Pulp Washing

The aim of this thesis was to produce information for the estimation of the flow balance of wood resin in mechanical pulping and to demonstrate the possibilities for improving the efficiency of deresination in practice. It was observed that chemical changes in wood resin take place only during peroxide bleaching, a significant amount of water dispersed wood resin is retained in the pulp mat during dewatering and the amount of wood resin in the solid phase of the process filtrates is very small. On the basis of this information there exist three parameters related to behaviour of wood resin that determine the flow balance in the process: 1. The liberation of wood resin to the pulp water phase 2. Theretention of water dispersed wood resin in dewatering 3. The proportion of wood resin degraded in the peroxide bleaching The effect of different factors on these parameters was evaluated with the help of laboratory studies and a literature survey. Also, information related to the values of these parameters in existing processes was obtained in mill measurements. With the help of this information, it was possible to evaluate the deresination efficiency and the effect of different factors on this efficiency in a pulping plant that produced low-freeness mechanical pulp. This evaluation showed that the wood resin content of mechanical pulp can be significantly decreased if there exists, in the process, a peroxide bleaching and subsequent washing stage. In the case of an optimal process configuration, as high as a 85 percent deresination efficiency seems to be possible with a water usage level of 8 m3/o.d.t.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Aplicació d'algoritmes genètics en l'optimització dels processos de fabricació del paper

La creciente preocupación y concienciación de la sociedad respecto el medio ambiente, y en consecuencia la legislación y regulaciones generadas inducen a la modificación de los procesos productivos existentes en la industria química. Las configuraciones iniciales deben modificarse para conseguir una mayor integración de procesos. Para este fin se han creado y desarrollado diferentes metodologías que deben facilitar la tarea a los responsables del rediseño. El desarrollo de una metodología y herramientas complementarias es el principal objetivo de la investigación aquí presentada, especialmente centrada en el desarrollo y la aplicación de una metodología de optimización de procesos. Esta metodología de optimización se aplica sobre configuraciones de proceso existentes y pretende encontrar nuevas configuraciones viables según los objetivos de optimización fijados. La metodología tiene dos partes diferenciadas: la primera se basa en un simulador de procesos comercial y la segunda es la técnica de optimización propiamente dicha. La metodología se inicia con la elaboración de una simulación convenientemente validada que reproduzca el proceso existente, en este caso una papelera no integrada que produce papel estucado de calidad, para impresión. A continuación la técnica de optimización realiza una búsqueda dentro del dominio de los posibles resultados, en busca de los mejores resultados que satisfazcan plenamente los objetivos planteados. Dicha técnica de optimización está basada en los algoritmos genéticos como herramienta de búsqueda, junto a un subprograma basado en técnicas de programación matemática para el cálculo de resultados. Un número reducido de resultados son finalmente escogidos y utilizados para modificar la simulación existente fijando la redistribución de los flujos del proceso. Los resultados de la simulación del proceso determinan en último caso la viabilidad técnica de cada reconfiguración planteada. En el proceso de optimización, los objetivos están definidos en una función objetivo dentro de la técnica de optimización. Dicha función rige la búsqueda de resultados. La función objetivo puede ser individual o una combinación de objetivos. En el presente caso, la función persigue una minimización del consumo de agua y una minimización de la pérdida de materia prima. La optimización se realiza bajo restricciones para alcanzar este objetivo combinado en forma de una solución de compromiso. Producto de la aplicación de esta metodología se han obtenido resultados interesantes que significan una mejora del cierre de circuitos y un ahorro de materia prima, sin comprometer al mismo tiempo la operabilidad del proceso producto ni la calidad del papel.

Catalysts and processes for next-generation H2 production

The present study is focused on the development of new VIII group metal on CeO2 – ZrO2 (CZO) catalyst to be used in reforming reaction for syngas production. The catalyst are tested in the oxyreforming process, extensively studied by Barbera [44] in a new multistep process configuration, with intermediate H2 membrane separation, that can be carried out at lower temperature (750°C) with respect the reforming processes (900 – 1000°C). In spite of the milder temperatures, the oxy-reforming conditions (S/C = 0.7; O2/C = 0.21) remain critical regarding the deactivation problems mainly deriving from thermal sintering and carbon formation phenomena. The combination of the high thermal stability characterizing the ZrO2, with the CeO2 redox properties, allows the formation of stable mixed oxide system with high oxygen mobility. This feature can be exploited in order to contrast the carbon deposition on the active metal surface through the oxidation of the carbon by means of the mobile oxygen atoms available at the surface of the CZO support. Ce0.5Zr0.5O2 is the phase claimed to have the highest oxygen mobility but its formation is difficult through classical synthesis (co-precipitation), hence a water-in-oil microemulsion method is, widely studied and characterized. Two methods (IWI and bulk) for the insertion of the active metal (Rh, Ru, Ni) are followed and their effects, mainly related to the metal stability and dispersion on the support, are discussed, correlating the characterization with the catalytic activity. Different parameters (calcination and reduction temperatures) are tuned to obtain the best catalytic system both in terms of activity and stability. Interesting results are obtained with impregnated and bulk catalysts, the latter representing a new class of catalysts. The best catalysts are also tested in a low temperature (350 – 500°C) steam reforming process and preliminary tests with H2 membrane separation have been also carried out.

A new strategy for selecting and evaluating physical solvents for gas absorption

This work describes how the physical properties of a solvent affect the design variables of a physical gas absorption process. The role of every property in determining the capital and the running cost of a process has been specified. Direct mathematical relationships have been formulated between every item of capital or running cost and the properties which are related to that item. The accuracy of the equations formulated has been checked by comparing their outcome with some actual design data. A good agreement has been found. The equations formulated may be used to evaluate on the basis of economics any suggested new solvents. A group of solvents were selected for evaluation. Their physical properties were estimated or collected as experimental data. The selected ones include three important solvents, the first is polyethylene glycol dimethyl ether (Selexol) which represents the currently most successful one, The other two solvents are acetonyl acetone (B2) and n-formyl morpholine which have been suggested previously as potential credible alternatives to the current ones. The important characteristics of: acetonyl acetone are its high solubility and its low viscosity, while the n-formyl morpholine is characterised by its low vapour pressure and its high selectivity. It was found that acetonyl acetone (B2) is the most attractive solvent for commercial applications particularly for process configurations that:include heat exchangers and strippers. The effect of the process configuration on the selected solvent was investigated in detail and it was found that there is no universal solvent which is the best for any process configuration, but that there is a best solvent for a given process configuration. In previous work, acetonyl acetone was suggested as a commercially promising physical solvent. That suggestion was not fully based on experimental measurement of all the physical properties. The viscosity of acetonyl acetone and its solubility at 1 atm were measured but the vapour pressure and the solubility of C02 and CH4 at high pressure were predicted. In this work, the solubilities of C02, CH4 and C3H8 in acetenyl acetone were measured for a partial pressure range of (2 ~ 22) bar at 25°C, The vapour pressure of this solvent was also measured, and the Antoine equation was formulated from tbe experimental data. The experimental data were found to be not In agreement with the predicted ones, so acetonyl acetone was re-evaluated according to the experimental data. It was found that this solvent can be recommended for further trials in a pilot plant study or for small scale commercial units.

Assessment of naproxen adsorption on bone char in aqueous solutions using batch and fixed-bed processes

An integrated analysis of naproxen adsorption on bone char in batch and packed-bed column conditions has been performed. Kinetic, thermodynamic and breakthrough parameters have been calculated using adsorption models and artificial neural networks. Results show that naproxen removal using bone char in batch conditions is a feasible and effective process, which could involve electrostatic and non-electrostatic interactions depending mainly on pH conditions. However, the application of packed-bed column for naproxen adsorption on bone char is not effective for the treatment of diluted solutions due to the low degree of adsorbent utilization (below 4%) at tested operating conditions. The proposed mechanism for naproxen removal using bone char could include a complexation process via phosphate and naproxen, hydrogen bonding and the possibility of hydrophobic interactions via π–π electron. This study highlights the relevance of performing an integrated analysis of adsorbent effectiveness in batch and dynamic conditions to establish the best process configuration for the removal of emerging water pollutants such as pharmaceuticals.

Modeling and developing a customer-oriented configuration process in a mass customization environment

In this thesis the main objective is to examine and model configuration system and related processes. When and where configuration information is created in product development process and how it is utilized in order-delivery process? These two processes are the essential part of the whole configuration system from the information point of view. Empirical part of the work was done as a constructive research inside a company that follows a mass customization approach. Data models and documentation are created for different development stages of the configuration system. A base data model already existed for new structures and relations between these structures. This model was used as the basis for the later data modeling work. Data models include different data structures, their key objects and attributes, and relations between. Representation of configuration rules for the to-be configuration system was defined as one of the key focus point. Further, it is examined how the customer needs and requirements information can be integrated into the product development process. Requirements hierarchy and classification system is presented. It is shown how individual requirement specifications can be connected for physical design structure via features by developing the existing base data model further.

Configuration management process improvement : a case study of a Pan-Nordic insurance company

Configuration management is often seen as an enabler for the main IT Service Management (ITSM) processes such as Incident and Problem management. A decent level of quality of IT configuration data is required in order to carry out routines of these processes. This case study examines the state of configuration management in a multinational organization and aims at identification of methods for its improvement. The author has stayed five months with this company in order to collect different sources of evidence and to make observations. The main source of data for this study is interviews with some of the key employees of the assigned organization who are involved into the ITSM processes. This study concludes the maturity level of the existing configuration management process to be repeatable but intuitive, and outlines the principal requirements for its improvement. A match between the requirements identified in the organization and the requirements stated in the ISO/IEC 20000 standard indicates the possibility of adopting ITIL guidelines as a method for configuration management process improvement. The outcome of the study presents a set of recommendations for improvement that considers the process, the information model and the information system for configuration management in the case organization.

A stochastic shift model for economically designed charts constrained by the process stage configuration

An economic model including the labor resource and the process stage configuration is proposed to design g charts allowing for all the design parameters to be varied in an adaptive way. A random shift size is considered during the economic design selection. The results obtained for a benchmark of 64 process stage scenarios show that the activities configuration and some process operating parameters influence the selection of the best control chart strategy: to model the random shift size, its exact distribution can be approximately fitted by a discrete distribution obtained from a relatively small sample of historical data. However, an accurate estimation of the inspection costs associated to the SPC activities is far from being achieved. An illustrative example shows the implementation of the proposed economic model in a real industrial case. (C) 2011 Elsevier B.V. All rights reserved.

Configuration management and product lines to enhance the replication process in software engineering

This research is concerned with the experimental software engineering area, specifically experiment replication. Replication has traditionally been viewed as a complex task in software engineering. This is possibly due to the present immaturity of the experimental paradigm applied to software development. Researchers usually use replication packages to replicate an experiment. However, replication packages are not the solution to all the information management problems that crop up when successive replications of an experiment accumulate. This research borrows ideas from the software configuration management and software product line paradigms to support the replication process. We believe that configuration management can help to manage and administer information from one replication to another: hypotheses, designs, data analysis, etc. The software product line paradigm can help to organize and manage any changes introduced into the experiment by each replication. We expect the union of the two paradigms in replication to improve the planning, design and execution of further replications and their alignment with existing replications. Additionally, this research work will contribute a web support environment for archiving information related to different experiment replications. Additionally, it will provide flexible enough information management support for running replications with different numbers and types of changes. Finally, it will afford massive storage of data from different replications. Experimenters working collaboratively on the same experiment must all have access to the different experiments.

Using configuration management and product line software paradigms to support the experimentation process in software engineering.

There is no empirical evidence whatsoever to support most of the beliefs on which software construction is based. We do not yet know the adequacy, limits, qualities, costs and risks of the technologies used to develop software. Experimentation helps to check and convert beliefs and opinions into facts. This research is concerned with the replication area. Replication is a key component for gathering empirical evidence on software development that can be used in industry to build better software more efficiently. Replication has not been an easy thing to do in software engineering (SE) because the experimental paradigm applied to software development is still immature. Nowadays, a replication is executed mostly using a traditional replication package. But traditional replication packages do not appear, for some reason, to have been as effective as expected for transferring information among researchers in SE experimentation. The trouble spot appears to be the replication setup, caused by version management problems with materials, instruments, documents, etc. This has proved to be an obstacle to obtaining enough details about the experiment to be able to reproduce it as exactly as possible. We address the problem of information exchange among experimenters by developing a schema to characterize replications. We will adapt configuration management and product line ideas to support the experimentation process. This will enable researchers to make systematic decisions based on explicit knowledge rather than assumptions about replications. This research will output a replication support web environment. This environment will not only archive but also manage experimental materials flexibly enough to allow both similar and differentiated replications with massive experimental data storage. The platform should be accessible to several research groups working together on the same families of experiments.

Multiclass Hammersley-Aldous-Diaconis process and multiclass-customer queues

In the Hammersley-Aldous-Diaconis process, infinitely many particles sit in R and at most one particle is allowed at each position. A particle at x, whose nearest neighbor to the right is at y, jumps at rate y - x to a position uniformly distributed in the interval (x, y). The basic coupling between trajectories with different initial configuration induces a process with different classes of particles. We show that the invariant measures for the two-class process can be obtained as follows. First, a stationary M/M/1 queue is constructed as a function of two homogeneous Poisson processes, the arrivals with rate, and the (attempted) services with rate rho > lambda Then put first class particles at the instants of departures (effective services) and second class particles at the instants of unused services. The procedure is generalized for the n-class case by using n - 1 queues in tandem with n - 1 priority types of customers. A multi-line process is introduced; it consists of a coupling (different from Liggett's basic coupling), having as invariant measure the product of Poisson processes. The definition of the multi-line process involves the dual points of the space-time Poisson process used in the graphical construction of the reversed process. The coupled process is a transformation of the multi-line process and its invariant measure is the transformation described above of the product measure.

E-contracting with price configuration for Web services and QoS

The large amount of information in electronic contracts hampers their establishment due to high complexity. An approach inspired in Software Product Line (PL) and based on feature modelling was proposed to make this process more systematic through information reuse and structuring. By assessing the feature-based approach in relation to a proposed set of requirements, it was showed that the approach does not allow the price of services and of Quality of Services (QoS) attributes to be considered in the negotiation and included in the electronic contract. Thus, this paper also presents an extension of such approach in which prices and price types associated to Web services and QoS levels are applied. An extended toolkit prototype is also presented as well as an experiment example of the proposed approach.

Characterization of micro-bubble size distribution and flow configuration in DAF contact zone by a non-intrusive image analysis system and tracer tests

This paper aims to investigate the influence of some dissolved air flotation (DAF) process variables (specifically: the hydraulic detention time in the contact zone and the supplied dissolved air concentration) and the pH values, as pretreatment chemical variables, on the micro-bubble size distribution (BSD) in a DAF contact zone. This work was carried out in a pilot plant where bubbles were measured by an appropriate non-intrusive image acquisition system. The results show that the obtained diameter ranges were in agreement with values reported in the literature (10-100mm), quite independently of the investigated conditions. The linear average diameter varied from 20 to 30mm, or equivalently, the Sauter (d(3,2)) diameter varied from 40 to 50mm. In all investigated conditions, D(50) was between 75% and 95%. The BSD might present different profile (with a bimodal curve trend), however, when analyzing the volumetric frequency distribution (in some cases with the appearance of peaks in diameters ranging from 90-100mm). Regarding volumetric frequency analysis, all the investigated parameters can modify the BSD in DAF contact zone after the release point, thus potentially causing changes in DAF kinetics. This finding prompts further research in order to verify the effect of these BSD changes on solid particle removal efficiency by DAF.