Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Modeling of Liquid-Solid Flow in Industrial Scale

In the present work, liquid-solid flow in industrial scale is modeled using the commercial software of Computational Fluid Dynamics (CFD) ANSYS Fluent 14.5. In literature, there are few studies on liquid-solid flow in industrial scale, but any information about the particular case with modified geometry cannot be found. The aim of this thesis is to describe the strengths and weaknesses of the multiphase models, when a large-scale application is studied within liquid-solid flow, including the boundary-layer characteristics. The results indicate that the selection of the most appropriate multiphase model depends on the flow regime. Thus, careful estimations of the flow regime are recommended to be done before modeling. The computational tool is developed for this purpose during this thesis. The homogeneous multiphase model is valid only for homogeneous suspension, the discrete phase model (DPM) is recommended for homogeneous and heterogeneous suspension where pipe Froude number is greater than 1.0, while the mixture and Eulerian models are able to predict also flow regimes, where pipe Froude number is smaller than 1.0 and particles tend to settle. With increasing material density ratio and decreasing pipe Froude number, the Eulerian model gives the most accurate results, because it does not include simplifications in Navier-Stokes equations like the other models. In addition, the results indicate that the potential location of erosion in the pipe depends on material density ratio. Possible sedimentation of particles can cause erosion and increase pressure drop as well. In the pipe bend, especially secondary flows, perpendicular to the main flow, affect the location of erosion.

The Effect of Plant Closures on Market Value: Empirical Evidence from Pulp and Paper Industry 2004-2012

The aim of this study was to research how plant closure announcements affect the market value of the largest pulp and paper industry companies in the world. Also the effect of announcements on competitors was researched and whether the location of plants, timing, reasons for the closures, and characteristics of the closing firms and competitors have an impact on the results. The overall sample included 57 events in the years 2004-2012 and event study was used as a research method. Main theories were signaling theory and spillover effect. According to empirical results, investors consider plant closure announcements as a positive signal for market value. The spillover effect on competitors was, on average, positive and characteristics of the firms and closures had an effect on the results. Furthermore, the market generally predicted the closures and overreacted to them on the announcement day and after it. It is possible for corporate management and investors to learn from the results and use them as support for their decision making.

Stiffness based trajectory planning and feedforward based vibration suppression control of parallel robot machines

The dissertation proposes two control strategies, which include the trajectory planning and vibration suppression, for a kinematic redundant serial-parallel robot machine, with the aim of attaining the satisfactory machining performance. For a given prescribed trajectory of the robot's end-effector in the Cartesian space, a set of trajectories in the robot's joint space are generated based on the best stiffness performance of the robot along the prescribed trajectory. To construct the required system-wide analytical stiffness model for the serial-parallel robot machine, a variant of the virtual joint method (VJM) is proposed in the dissertation. The modified method is an evolution of Gosselin's lumped model that can account for the deformations of a flexible link in more directions. The effectiveness of this VJM variant is validated by comparing the computed stiffness results of a flexible link with the those of a matrix structural analysis (MSA) method. The comparison shows that the numerical results from both methods on an individual flexible beam are almost identical, which, in some sense, provides mutual validation. The most prominent advantage of the presented VJM variant compared with the MSA method is that it can be applied in a flexible structure system with complicated kinematics formed in terms of flexible serial links and joints. Moreover, by combining the VJM variant and the virtual work principle, a systemwide analytical stiffness model can be easily obtained for mechanisms with both serial kinematics and parallel kinematics. In the dissertation, a system-wide stiffness model of a kinematic redundant serial-parallel robot machine is constructed based on integration of the VJM variant and the virtual work principle. Numerical results of its stiffness performance are reported. For a kinematic redundant robot, to generate a set of feasible joints' trajectories for a prescribed trajectory of its end-effector, its system-wide stiffness performance is taken as the constraint in the joints trajectory planning in the dissertation. For a prescribed location of the end-effector, the robot permits an infinite number of inverse solutions, which consequently yields infinite kinds of stiffness performance. Therefore, a differential evolution (DE) algorithm in which the positions of redundant joints in the kinematics are taken as input variables was employed to search for the best stiffness performance of the robot. Numerical results of the generated joint trajectories are given for a kinematic redundant serial-parallel robot machine, IWR (Intersector Welding/Cutting Robot), when a particular trajectory of its end-effector has been prescribed. The numerical results show that the joint trajectories generated based on the stiffness optimization are feasible for realization in the control system since they are acceptably smooth. The results imply that the stiffness performance of the robot machine deviates smoothly with respect to the kinematic configuration in the adjacent domain of its best stiffness performance. To suppress the vibration of the robot machine due to varying cutting force during the machining process, this dissertation proposed a feedforward control strategy, which is constructed based on the derived inverse dynamics model of target system. The effectiveness of applying such a feedforward control in the vibration suppression has been validated in a parallel manipulator in the software environment. The experimental study of such a feedforward control has also been included in the dissertation. The difficulties of modelling the actual system due to the unknown components in its dynamics is noticed. As a solution, a back propagation (BP) neural network is proposed for identification of the unknown components of the dynamics model of the target system. To train such a BP neural network, a modified Levenberg-Marquardt algorithm that can utilize an experimental input-output data set of the entire dynamic system is introduced in the dissertation. Validation of the BP neural network and the modified Levenberg- Marquardt algorithm is done, respectively, by a sinusoidal output approximation, a second order system parameters estimation, and a friction model estimation of a parallel manipulator, which represent three different application aspects of this method.

The Cycle Times of Working Capital: Financial Value Chain Analysis Method

Interest towards working capital management increased among practitioners and researchers because the financial crisis of 2008 caused the deterioration of the general financial situation. The importance of managing working capital effectively increased dramatically during the financial crisis. On one hand, companies highlighted the importance of working capital management as part of short-term financial management to overcome funding difficulties. On the other hand, in academia, it has been highlighted the need to analyze working capital management from a wider perspective namely from the value chain perspective. Previously, academic articles mostly discussed working capital management from a company-centered perspective. The objective of this thesis was to put working capital management in a wider and more academic perspective and present case studies of the value chains of industries as instrumental in theoretical contributions and practical contributions as complementary to theoretical contributions and conclusions. The principal assumption of this thesis is that selffinancing of value chains can be established through effective working capital management. Thus, the thesis introduces the financial value chain analysis method which is employed in the empirical studies. The effectiveness of working capital management of the value chains is studied through the cycle time of working capital. The financial value chain analysis method employed in this study is designed for considering value chain level phenomena. This method provides a holistic picture of the value chain through financial figures. It extends the value chain analysis to the industry level. Working capital management is studied by the cash conversion cycle that measures the length (days) of time a company has funds tied up in working capital, starting from the payment of purchases to the supplier and ending when remittance of sales is received from the customers. The working capital management practices employed in the automotive, pulp and paper and information and communication technology industries have been studied in this research project. Additionally, the Finnish pharmaceutical industry is studied to obtain a deeper understanding of the working capital management of the value chain. The results indicate that the cycle time of working capital is constant in the value chain context over time. The cash conversion cycle of automotive, pulp and paper, and ICT industries are on average 70, 60 and 40 days, respectively. The difference is mainly a consequence of the different cycle time of inventories. The financial crisis of 2008 affected the working capital management of the industries similarly. Both the cycle time of accounts receivable and accounts payable increased between 2008 and 2009. The results suggest that the companies of the automotive, pulp and paper and ICT value chains were not able to self-finance. Results do not indicate the improvement of value chains position in regard to working capital management either. The findings suggest that companies operating in the Finnish pharmaceutical industry are interested in developing their own working capital management, but collaboration with the value chain partners is not considered interesting. Competition no longer occurs between individual companies, but between value chains. Therefore the financial value chain analysis method introduced in this thesis has the potential to support value chains in improving their competitiveness.

Advanced analysis and design methods for preparative chromatographic separation processes

Preparative liquid chromatography is one of the most selective separation techniques in the fine chemical, pharmaceutical, and food industries. Several process concepts have been developed and applied for improving the performance of classical batch chromatography. The most powerful approaches include various single-column recycling schemes, counter-current and cross-current multi-column setups, and hybrid processes where chromatography is coupled with other unit operations such as crystallization, chemical reactor, and/or solvent removal unit. To fully utilize the potential of stand-alone and integrated chromatographic processes, efficient methods for selecting the best process alternative as well as optimal operating conditions are needed. In this thesis, a unified method is developed for analysis and design of the following singlecolumn fixed bed processes and corresponding cross-current schemes: (1) batch chromatography, (2) batch chromatography with an integrated solvent removal unit, (3) mixed-recycle steady state recycling chromatography (SSR), and (4) mixed-recycle steady state recycling chromatography with solvent removal from fresh feed, recycle fraction, or column feed (SSR–SR). The method is based on the equilibrium theory of chromatography with an assumption of negligible mass transfer resistance and axial dispersion. The design criteria are given in general, dimensionless form that is formally analogous to that applied widely in the so called triangle theory of counter-current multi-column chromatography. Analytical design equations are derived for binary systems that follow competitive Langmuir adsorption isotherm model. For this purpose, the existing analytic solution of the ideal model of chromatography for binary Langmuir mixtures is completed by deriving missing explicit equations for the height and location of the pure first component shock in the case of a small feed pulse. It is thus shown that the entire chromatographic cycle at the column outlet can be expressed in closed-form. The developed design method allows predicting the feasible range of operating parameters that lead to desired product purities. It can be applied for the calculation of first estimates of optimal operating conditions, the analysis of process robustness, and the early-stage evaluation of different process alternatives. The design method is utilized to analyse the possibility to enhance the performance of conventional SSR chromatography by integrating it with a solvent removal unit. It is shown that the amount of fresh feed processed during a chromatographic cycle and thus the productivity of SSR process can be improved by removing solvent. The maximum solvent removal capacity depends on the location of the solvent removal unit and the physical solvent removal constraints, such as solubility, viscosity, and/or osmotic pressure limits. Usually, the most flexible option is to remove solvent from the column feed. Applicability of the equilibrium design for real, non-ideal separation problems is evaluated by means of numerical simulations. Due to assumption of infinite column efficiency, the developed design method is most applicable for high performance systems where thermodynamic effects are predominant, while significant deviations are observed under highly non-ideal conditions. The findings based on the equilibrium theory are applied to develop a shortcut approach for the design of chromatographic separation processes under strongly non-ideal conditions with significant dispersive effects. The method is based on a simple procedure applied to a single conventional chromatogram. Applicability of the approach for the design of batch and counter-current simulated moving bed processes is evaluated with case studies. It is shown that the shortcut approach works the better the higher the column efficiency and the lower the purity constraints are.

Forecasting financial weather - can we foresee market sentiment? Quantitative analysis of nodal prices in the New Zealand Electricity Spot Market

Time series of hourly electricity spot prices have peculiar properties. Electricity is by its nature difficult to store and has to be available on demand. There are many reasons for wanting to understand correlations in price movements, e.g. risk management purposes. The entire analysis carried out in this thesis has been applied to the New Zealand nodal electricity prices: offer prices (from 29 May 2002 to 31 March 2009) and final prices (from 1 January 1999 to 31 March 2009). In this paper, such natural factors as location of the node and generation type in the node that effects the correlation between nodal prices have been reviewed. It was noticed that the geographical factor affects the correlation between nodes more than others. Therefore, the visualisation of correlated nodes was done. However, for the offer prices the clear separation of correlated and not correlated nodes was not obtained. Finally, it was concluded that location factor most strongly affects correlation of electricity nodal prices; problems in visualisation probably associated with power losses when the power is transmitted over long distance.

Computational studies of deformation in stainless steel rings due to torch heating

A support ring of AISI 304L stainless steel that holds vertical, parallel wires arranged in a circle forming a cylinder is studied. The wires are attached to the ring with heat-induced shrinkage. When the ring is heated with a torch the heat affected zone tries to expand while the adjacent cool structure obstructs the expansion causing upsetting. During cooling, the ring shrinks smaller than its original size clamping the wires. The most important requirement for the ring is that it should be as round as possible and the deformations should occur as overall shrinkage in the ring diameter. A three-dimensional nonlinear transient sequential thermo-structural Abaqus model is used together with a Fortran code that enters the heat flux to each affected element. The local and overall deformations in one ring inflicted by the heating are studied with a small amount of inspection on residual stresses. A variety of different cases are chosen to be studied with the model constructed to provide directional knowledge; torch flux with the means of speed, location of the wires, heating location and structural factors. The decrease of heating speed increases heat flux that rises the temperature increasing shrinkage. In a single progressive heating uneven distribution of shrinkage appears to the start/end region that can be partially fixed with using speeded heating’s to strengthen the heating of that region. Location of the wires affect greatly to the caused shrinkage unlike heating location. The ring structure affects also greatly to the shrinkage; smaller diameter, bigger ring height, thinner thickness and greater number of wires increase shrinkage.

Thick Section Laser Beam Welding of Structural Steels: Methods for Improving Welding Efficiency

Laser beam welding (LBW) is applicable for a wide range of industrial sectors and has a history of fifty years. However, it is considered an unusual method with applications typically limited to welding of thin sheet metal. With a new generation of high power lasers there has been a renewed interest in thick section LBW (also known as keyhole laser welding). There was a growing body of publications during 2001-2011 that indicates an increasing interest in laser welding for many industrial applications, and in last ten years, an increasing number of studies have examined the ways to increase the efficiency of the process. Expanding the thickness range and efficiency of LBW makes the process a possibility for industrial applications dealing with thick metal welding: shipbuilding, offshore structures, pipelines, power plants and other industries. The advantages provided by LBW, such as high process speed, high productivity, and low heat input, may revolutionize these industries and significantly reduce the process costs. The research to date has focused on either increasing the efficiency via optimizing process parameters, or on the process fundamentals, rather than on process and workpiece modifications. The argument of this thesis is that the efficiency of the laser beam process can be increased in a straightforward way in the workshop conditions. Throughout this dissertation, the term “efficiency” is used to refer to welding process efficiency, specifically, an increase in efficiency refers an increase in weld’s penetration depth without increasing laser power level or decreasing welding speed. These methods are: modifications of the workpiece – edge surface roughness and air gap between the joining plates; modification of the ambient conditions – local reduction of the pressure in the welding zone; modification of the welding process – preheating of the welding zone. Approaches to improve the efficiency are analyzed and compared both separately and combined. These experimentally proven methods confirm previous findings and contribute additional evidence which expand the opportunities for laser beam welding applications. The focus of this research was primarily on the effects of edge surface roughness preparation and pre-set air gap between the plates on weld quality and penetration depth. To date, there has been no reliable evidence that such modifications of the workpiece give a positive effect on the welding efficiency. Other methods were tested in combination with the two methods mentioned above. The most promising - combining with reduced pressure method - resulted in at least 100% increase in efficiency. The results of this thesis support the idea that joining those methods in one modified process will provide the modern engineering with a sufficient tool for many novel applications with potential benefits to a range of industries.

Feasibility of industrial implementation of laser cutting into paper making machine

Laser cutting implementation possibilities into paper making machine was studied as the main objective of the work. Laser cutting technology application was considered as a replacement tool for conventional cutting methods used in paper making machines for longitudinal cutting such as edge trimming at different paper making process and tambour roll slitting. Laser cutting of paper was tested in 70’s for the first time. Since then, laser cutting and processing has been applied for paper materials with different level of success in industry. Laser cutting can be employed for longitudinal cutting of paper web in machine direction. The most common conventional cutting methods include water jet cutting and rotating slitting blades applied in paper making machines. Cutting with CO2 laser fulfils basic requirements for cutting quality, applicability to material and cutting speeds in all locations where longitudinal cutting is needed. Literature review provided description of advantages, disadvantages and challenges of laser technology when it was applied for cutting of paper material with particular attention to cutting of moving paper web. Based on studied laser cutting capabilities and problem definition of conventional cutting technologies, preliminary selection of the most promising application area was carried out. Laser cutting (trimming) of paper web edges in wet end was estimated to be the most promising area where it can be implemented. This assumption was made on the basis of rate of web breaks occurrence. It was found that up to 64 % of total number of web breaks occurred in wet end, particularly in location of so called open draws where paper web was transferred unsupported by wire or felt. Distribution of web breaks in machine cross direction revealed that defects of paper web edge was the main reason of tearing initiation and consequent web break. The assumption was made that laser cutting was capable of improvement of laser cut edge tensile strength due to high cutting quality and sealing effect of the edge after laser cutting. Studies of laser ablation of cellulose supported this claim. Linear energy needed for cutting was calculated with regard to paper web properties in intended laser cutting location. Calculated linear cutting energy was verified with series of laser cutting. Practically obtained laser energy needed for cutting deviated from calculated values. This could be explained by difference in heat transfer via radiation in laser cutting and different absorption characteristics of dry and moist paper material. Laser cut samples (both dry and moist (dry matter content about 25-40%)) were tested for strength properties. It was shown that tensile strength and strain break of laser cut samples are similar to corresponding values of non-laser cut samples. Chosen method, however, did not address tensile strength of laser cut edge in particular. Thus, the assumption of improving strength properties with laser cutting was not fully proved. Laser cutting effect on possible pollution of mill broke (recycling of trimmed edge) was carried out. Laser cut samples (both dry and moist) were tested on the content of dirt particles. The tests revealed that accumulation of dust particles on the surface of moist samples can take place. This has to be taken into account to prevent contamination of pulp suspension when trim waste is recycled. Material loss due to evaporation during laser cutting and amount of solid residues after cutting were evaluated. Edge trimming with laser would result in 0.25 kg/h of solid residues and 2.5 kg/h of lost material due to evaporation. Schemes of laser cutting implementation and needed laser equipment were discussed. Generally, laser cutting system would require two laser sources (one laser source for each cutting zone), set of beam transfer and focusing optics and cutting heads. In order to increase reliability of system, it was suggested that each laser source would have double capacity. That would allow to perform cutting employing one laser source working at full capacity for both cutting zones. Laser technology is in required level at the moment and do not require additional development. Moreover, capacity of speed increase is high due to availability high power laser sources what can support the tendency of speed increase of paper making machines. Laser cutting system would require special roll to maintain cutting. The scheme of such roll was proposed as well as roll integration into paper making machine. Laser cutting can be done in location of central roll in press section, before so-called open draw where many web breaks occur, where it has potential to improve runability of a paper making machine. Economic performance of laser cutting was done as comparison of laser cutting system and water jet cutting working in the same conditions. It was revealed that laser cutting would still be about two times more expensive compared to water jet cutting. This is mainly due to high investment cost of laser equipment and poor energy efficiency of CO2 lasers. Another factor is that laser cutting causes material loss due to evaporation whereas water jet cutting almost does not cause material loss. Despite difficulties of laser cutting implementation in paper making machine, its implementation can be beneficial. The crucial role in that is possibility to improve cut edge strength properties and consequently reduce number of web breaks. Capacity of laser cutting to maintain cutting speeds which exceed current speeds of paper making machines what is another argument to consider laser cutting technology in design of new high speed paper making machines.