Modeling of non-isothermalvapor membrane separation with thermodynamic models and generalized mass transfer equations

A rigorous unit operation model is developed for vapor membrane separation. The new model is able to describe temperature, pressure, and concentration dependent permeation as wellreal fluid effects in vapor and gas separation with hydrocarbon selective rubbery polymeric membranes. The permeation through the membrane is described by a separate treatment of sorption and diffusion within the membrane. The chemical engineering thermodynamics is used to describe the equilibrium sorption of vapors and gases in rubbery membranes with equation of state models for polymeric systems. Also a new modification of the UNIFAC model is proposed for this purpose. Various thermodynamic models are extensively compared in order to verify the models' ability to predict and correlate experimental vapor-liquid equilibrium data. The penetrant transport through the selective layer of the membrane is described with the generalized Maxwell-Stefan equations, which are able to account for thebulk flux contribution as well as the diffusive coupling effect. A method is described to compute and correlate binary penetrant¿membrane diffusion coefficients from the experimental permeability coefficients at different temperatures and pressures. A fluid flow model for spiral-wound modules is derived from the conservation equation of mass, momentum, and energy. The conservation equations are presented in a discretized form by using the control volume approach. A combination of the permeation model and the fluid flow model yields the desired rigorous model for vapor membrane separation. The model is implemented into an inhouse process simulator and so vapor membrane separation may be evaluated as an integralpart of a process flowsheet.

Valsystem i lilleputtar: pluralitet och diffusion

Abstract: Elections in lilliputs: plurality and diffusion

Diffusion av valsystem

Lectio praecursoria Åbo Akademi 1.2.2006

Particle transport method for convection-diffusion-reaction problems

Convective transport, both pure and combined with diffusion and reaction, can be observed in a wide range of physical and industrial applications, such as heat and mass transfer, crystal growth or biomechanics. The numerical approximation of this class of problemscan present substantial difficulties clue to regions of high gradients (steep fronts) of the solution, where generation of spurious oscillations or smearing should be precluded. This work is devoted to the development of an efficient numerical technique to deal with pure linear convection and convection-dominated problems in the frame-work of convection-diffusion-reaction systems. The particle transport method, developed in this study, is based on using rneshless numerical particles which carry out the solution along the characteristics defining the convective transport. The resolution of steep fronts of the solution is controlled by a special spacial adaptivity procedure. The serni-Lagrangian particle transport method uses an Eulerian fixed grid to represent the solution. In the case of convection-diffusion-reaction problems, the method is combined with diffusion and reaction solvers within an operator splitting approach. To transfer the solution from the particle set onto the grid, a fast monotone projection technique is designed. Our numerical results confirm that the method has a spacial accuracy of the second order and can be faster than typical grid-based methods of the same order; for pure linear convection problems the method demonstrates optimal linear complexity. The method works on structured and unstructured meshes, demonstrating a high-resolution property in the regions of steep fronts of the solution. Moreover, the particle transport method can be successfully used for the numerical simulation of the real-life problems in, for example, chemical engineering.

Mobile Communications within the European Union: The Role of Location in the Evolution and Forecasting of the Diffusion Process

In the European Union, the importance of mobile communications was realized early on. The process of mobile communications becoming ubiquitous has taken time, as the innovation of mobile communications diffused into the society. The aim of this study is to find out how the evolution and spatial patterns of the diffusion of mobile communications within the European Union could be taken into account in forecasting the diffusion process. There is relatively lot of research of innovation diffusion on the individual (micro) andthe country (macro) level, if compared to the territorial level. Territorial orspatial diffusion refers either to the intra-country or inter-country diffusionof an innovation. In both settings, the dif- fusion of a technological innovation has gained scarce attention. This study adds knowledge of the diffusion between countries, focusing especially on the role of location in this process. The main findings of the study are the following: The penetration rates of the European Union member countries have become more even in the period of observation, from the year 1981 to 2000. The common digital GSM system seems to have hastened this process. As to the role of location in the diffusion process, neighboring countries have had similar diffusion processes. They can be grouped into three, the Nordic countries, the central and southern European countries, and the remote southern European countries. The neighborhood effect is also domi- nating in thegravity model which is used for modeling the adoption timing of the countries. The subsequent diffusion within a country, measured by the logistic model in Finland, is af- fected positively by its economic situation, and it seems to level off at some 92 %. Considering the launch of future mobile communications systemsusing a common standard should implicate an equal development between the countries. The launching time should be carefully selected as the diffusion is probably delayed in economic downturns. The location of a country, measured by distance, can be used in forecasting the adoption and diffusion. Fi- nally, the result of penetration rates becoming more even implies that in a relatively homoge- nous set of countries, such as the European Union member countries, the estimated final pene- tration of a single country can be used for approximating the penetration of the others. The estimated eventual penetration of Finland, some 92 %, should thus also be the eventual level for all the European Union countries and for the European Union as a whole.

Development of a Ceramic Membrane Filtration Equipment and Its Applicability for Different Wastewaters

In this thesis the membrane filtration equipment for plate type ceramic membranes was developed based on filtration results achieved with different kinds of wastewaters. The experiments were mainly made with pulp and board mill wastewaters, but some experiments were also made with a bore well water and a stone cutting mine wastewater. The ceramicmembranes used were alpha-alumina membranes with a pore size of 100 nm. Some ofthe membranes were coated with a gamma-alumina layer to reduce the membrane pore size to 10 nm, and some of them were modified with different metal oxides in order to change the surface properties of the membranes. The effects of operationparameters, such as cross-flow velocity, filtration pressure and backflushing on filtration performance were studied. The measured parameters were the permeateflux, the quality of the permeate, as well as the fouling tendency of the membrane. A dynamic membrane or a cake layer forming on top of the membrane was observed to decrease the flux and increase separa-tion of certain substances, especially at low cross-flow velocities. When the cross-flow velocities were increased the membrane properties became more important. Backflushing could also be used to decrease the thickness of the cake layer and thus it improved the permeate flux. However, backflushing can lead to a reduction of retentions in cases where the cake layer is improving them. The wastewater quality was important for the thickness of the dynamic membrane and the membrane pore size influenced the permeate flux. In general, the optimization of operation conditions is very important for the successful operation of a membrane filtration system. The filtration equipment with a reasonable range of operational conditions is necessary, especiallywhen different kinds of wastewaters are treated. This should be taken into account already in the development stage of a filtration equipment.

Effect of competitive situation and price on diffusion of mobile communications

Työn päätavoitteena oli selvittää hinnan ja kilpailutilanteen vaikutusta matkaviestinnän diffuusioon. Työn empiirinen osuus tarkasteli matkapuhelinliittymien hinnan vaikutusta liittymien diffuusioon sekä sitä, miten alan kilpailu on vaikuttanut matkaviestinnän hintatasoon. Työssä analysoitiin myös matkaviestinnän kilpailutilannetta Suomen markkinoilla. Tutkimuksen empiirinen aineisto kerättiin toissijaisista lähteistä, esimerkiksi EMC-tietokannasta. Tutkimus oli luonteeltaan kvantitatiivinen.Empiirisessä osassa käytetyt mallit oli muodostettu aikaisempien tutkimuksien perusteella. Regressioanalyysiä käytettiin arvioitaessa hinnan vaikutusta diffuusionopeuteen ja mahdollisten omaksujien määrään. Regressioanalyysissä sovellettiin ei-lineaarista mallia.Tutkimustulokset osoittivat, että tasaisesti laskevilla matkapuhelinliittymien sekä matkapuhelimien hinnoilla ei ole merkittävää vaikutusta matkaviestinnän diffuusioon. Myöskään kilpailutilanne ei ole vaikuttanut paljon matkaviestinnän yleiseen hintatasoon. Työn tulosten perusteella voitiin antaa myös muutamia toimenpide-ehdotuksia jatkotutkimuksia varten.

Predicting diffusion of innovations with self-organisation and machine learning

The main subject of this master's thesis was predicting diffusion of innovations. The prediction was done in a special case: product has been available in some countries, and based on its diffusion in those countries the prediction is done for other countries. The prediction was based on finding similar countries with Self-Organizing Map~(SOM), using parameters of countries. Parameters included various economical and social key figures. SOM was optimised for different products using two different methods: (a) by adding diffusion information of products to the country parameters, and (b) by weighting the country parameters based on their importance for the diffusion of different products. A novel method using Differential Evolution (DE) was developed to solve the latter, highly non-linear optimisation problem. Results were fairly good. The prediction method seems to be on a solid theoretical foundation. The results based on country data were good. Instead, optimisation for different products did not generally offer clear benefit, but in some cases the improvement was clearly noticeable. The weights found for the parameters of the countries with the developed SOM optimisation method were interesting, and most of them could be explained by properties of the products.

Factors Affecting the Forecasting Accuracy of Diffusion Models

Tutkielman tavoitteena oli tarkastella innovaatioiden leviämismallien ennustetarkkuuteen vaikuttavia tekijöitä. Tutkielmassa ennustettiin logistisella mallilla matkapuhelinliittymien leviämistä kolmessa Euroopan maassa: Suomessa, Ranskassa ja Kreikassa. Teoriaosa keskittyi innovaatioiden leviämisen ennustamiseen leviämismallien avulla. Erityisesti painotettiin mallien ennustuskykyä ja niiden käytettävyyttä eri tilanteissa. Empiirisessä osassa keskityttiin ennustamiseen logistisella leviämismallilla, joka kalibroitiin eri tavoin koostetuilla aikasarjoilla. Näin tehtyjä ennusteita tarkasteltiin tiedon kokoamistasojen vaikutusten selvittämiseksi. Tutkimusasetelma oli empiirinen, mikä sisälsi logistisen leviämismallin ennustetarkkuuden tutkimista otosdatan kokoamistasoa muunnellen. Leviämismalliin syötettävä data voidaan kerätä kuukausittain ja operaattorikohtaisesti vaikuttamatta ennustetarkkuuteen. Dataan on sisällytettävä leviämiskäyrän käännöskohta, eli pitkän aikavälin huippukysyntäpiste.

Business models enhancing the diffusion of mobile Internet in emerging markets

Tämän tutkimuksen päätavoitteena oli selvittää, millaiset liiketoimintamallit soveltuvat mobiilin internet-liiketoiminnan harjoittamiseen kehittyvillä markkinoilla. Tavoitteena oli myös selvittää tekijöitä, jotka vaikuttavat mobiilin internetin diffuusioon. Tutkimus tehtiin käyttäen sekä kvantitatiivista että kvalitatiivista tutkimusmenetelmää. Klusterianalyysin avulla 40 Euroopan maasta muodostettiin sisäisesti homogeenisiä maaklustereita. Näiden klustereiden avulla oli mahdollista suunnitella erityyppisille markkinoille soveltuvat liiketoimintamallit. Haastatteluissa selvitettiin asiantuntijoiden näkemyksiä tekijöistä, jotka vaikuttavat mobiilin internetin diffuusioon kehittyvillä markkinoilla. Tutkimuksessa saatiin selville, että tärkeimmät liiketoimintamallin elementit kehittyvillä markkinoilla ovat hinnoittelu, arvotarjooma ja arvoverkko. Puutteellisen kiinteän verkon todettiin olevan yksi tärkeimmistä mobiilin internetin diffuusiota edistävistä tekijöistä kehittyvillä markkinoilla.

Diffusion of Administrative Innovation: TQM Implementation and Effectiveness in a Global

The main objective of this dissertation is to create new knowledge on an administrative innovation, its adoption, diffusion and finally its effectiveness. In this dissertation the administrative innovation is approached through a widely utilized management philosophy, namely the total quality management (TQM) strategy. TQM operationalizes a self-assessment procedure, which is based on continual improvement principles and measuring the improvements. This dissertation also captures the theme of change management as it analyzes the adoption and diffusion of the administrative innovation. It identifies innovation characteristics as well as organisational and individual factors explaining the adoption and implementation. As a special feature, this study also explores the effectiveness of the innovation based on objective data. For studying the administrative innovation (TQM model), a multinational Case Company provides a versatile ground for a deep, longitudinal analysis. The Case Company started the adoption systematically in the mid 1980s in some of its units. As part of their strategic planning today, the procedure is in use throughout the entire global company. The empirical story begins from the innovation adoption decision that was made in the Case Company over 22 years ago. In order to be able to capture the right atmosphere and backgrounds leading to the adoption decision, key informants from that time were interviewed, since the main target was to clarify the dynamics of how an administrative innovation develops. In addition, archival material was collected and studied, available memos and data relating to the innovation, innovation adoption and later to the implementation contained altogether 20500 pages of documents. A survey was furthermore conducted at the end of 2006 focusing on questions related to the innovation, organization and leadership characteristics and the response rate totalled up to 54%. For measuring the effectiveness of the innovation implementation, the needed longitudinal objective performance data was collected. This data included the profit unit level experience of TQM, the development of the self assessment scores per profit unit and performance data per profit unit measured with profitability, productivity and customer satisfaction. The data covered the years 1995-2006. As a result, the prerequisites for the successful adoption of an administrative innovation were defined, such as the top management involvement, support of the change agents and effective tools for implementation and measurement. The factors with the greatest effect on the depth of the implementation were the timing of the adoption and formalization. The results also indicated that the TQM model does have an effect on the company performance measured with profitability, productivity and customer satisfaction. Consequently this thesis contributes to the present literature (i) by taking into its scope an administrative innovation and focusing on the whole innovation implementation process, from the adoption, through diffusion until its consequences, (ii) because the studied factors with an effect on the innovation adoption and diffusion are multifaceted and grouped into individual, organizational and environmental factors, and a strong emphasis is put on the role of the individual change agents and (iii) by measuring the depth and consistency of the administrative innovation. This deep analysis was possible due to the availability of longitudinal data with triangulation possibilities.

Role of Membrane Transporters, P-Glycoprotein and Mrp1, in The Placental Transfer of Drugs With Special Reference to Saquinavir and Quetiapine

Drug transporting membrane proteins are expressed in various human tissues and blood-tissue barriers, regulating the transfer of drugs, toxins and endogenous compounds into or out of the cells. Various in vitro and animal experiments suggest that P-glycoprotein (P-gp) forms a functional barrier between maternal and fetal blood circulation in the placenta thereby protecting the fetus from exposure to xenobiotics during pregnancy. The multidrug resistance-associated protein 1 (MRP1) is a relatively less studied transporter protein in the human placenta. The aim of this study series was to study the role of placental transporters, apical P-gp and basal MRP1, using saquinavir as a probe drug, and to study transfer of quetiapine and the role of P-gp in its transfer in the dually perfused human placenta/cotyledon. Furthermore, two ABCB1 (encoding P-gp) polymorphisms (c.3435C>T, p.Ile1145Ile and c.2677G>T/A, p.Ala893Ser/Thr) were studied to determine their impact on P-gp protein expression level and on the transfer of the study drugs. Also, the influence of the P-gp protein expression level on the transfer of the study drugs was addressed. Because P-gp and MRP1 are ATP-dependent drug-efflux pumps, it was studied whether exogenous ATP is needed for the function of ATP-dependent transporter in the present experimental model. The present results indicated that the addition of exogenous ATP was not necessary for transporter function in the perfused human placental cotyledon. Saquinavir and quetiapine were both found to cross the human placenta; transplacental transfer (TPTAUC %) for saquinavir was <0.5% and for quetiapine 3.7%. Pharmacologic blocking of P-gp led to disruption of the blood-placental barrier (BPB) and increased the placental transfer of P-gp substrate, saquinavir, into the fetal circulation by 6- to 8-fold. In reversed perfusions P-gp, MRP1 and possibly OATP2B1 had a negligible role in the fetal-to-maternal transfer of saquinavir. The TPTAUC % of saquinavir was about 100-fold greater from the fetal side to the maternal side compared with the maternal-to-fetal transfer. P-gp activity is not likely to modify the placental transfer of quetiapine. Higher P-gp protein expression levels were associated with the variant allele 3435T, but no correlation was found between the TPTAUC % of saquinavir and placental P-gp protein expression. The present results indicate that P-gp activity drastically affects the fetal exposure to saquinavir, and suggest that pharmacological blockade of the P-gp activity during pregnancy may pose an increased risk for adverse fetal outcome. The blockade of P-gp activity could be used in purpose to obtain higher drug concentration to the fetal side, for example, in prevention (to decrease virus transfer to fetal side) or in treating sick fetus.

Recovery of Hemicelluloses from Wood Hydrolysates by Membrane Filtration

Hemicelluloses are among the most important natural resources that contain polysaccharides. In this study the separation and purification of hemicelluloses from water extraction liquors containing wood hemicelluloses, lignin compounds and monosaccharide by using membrane filtration was investigated. The isolation of the hemicelluloses from the wood hydrolysates was performed in two steps: concentration of high molar mass hemicelluloses by ultrafiltration and separation of low molar mass hemicelluloses from monomeric sugars using tight ultrafiltration membranes. The purification of the retained hemicelluloses was performed by diafiltration. During the filtration experiments, the permeate flux through ultrafiltration and tight ultrafiltration membranes was relatively high. The fouling ability of the used membranes was relatively low. In our experiments, the retention of hemicelluloses using two filtration steps was almost complete. The separation of monosaccharides from hemicelluloses was relatively high and the purification of hemicelluloses by diafiltration was highly efficient. The separation of lignin from hemicelluloses was partially achieved. Diafiltration showed potential to purify retained hemicelluloses from lignin and other organics. The best separation of lignin from hemicelluloses in the first filtration step was obtained using the UC005 membrane. The GE-5 and ETNA01PP membranes showed potential to purify and separate lignin from hemicelluloses. However, the feed solution of the second filtration stages (from different ultrafiltration membranes) affected the permeate flux and the separation of various extracted compounds from hemicelluloses. The GE-5 and ETNA01PP membranes gave the efficient purification of the hemicelluloses when using diafiltration. Separation of degraded xylan from glucomannan (primary spruce hemicelluloses) was also possible using membrane filtration. The best separation was achieved using the GE-5 membrane. The retention of glucomannan was three times higher than xylan retention.

Fouling management and retention in nanofiltration of integrated paper mill effluents

Nanofiltration performance was studied with effluents from the pulp and paper industry and with model substances. The effect of filtration conditions and membrane properties on nanofiltration flux, retention, and fouling was investigated. Generally, the aim was to determine the parameters that influence nanofiltration efficiency and study how to carry out nanofiltration without fouling by controlling these parameters. The retentions of the nanofiltration membranes studied were considerably higher than those of tight ultrafiltration membranes, and the permeate fluxes obtained were approximately the same as those of tight ultrafiltration membranes. Generally, about 80% retentions of total carbon and conductivity were obtained during the nanofiltration experiments. Depending on the membrane and the filtration conditions, the retentions of monovalent ions (chloride) were between 80 and 95% in the nanofiltrations. An increase in pH improved retentions considerably and also the flux to some degree. An increase in pressure improved retention, whereas an increase in temperature decreased retention if the membrane retained the solute by the solution diffusion mechanism. In this study, more open membranes fouled more than tighter membranes due to higher concentration polarization and plugging of the membrane material. More irreversible fouling was measured for hydrophobic membranes. Electrostatic repulsion between the membrane and the components in the solution reduced fouling but did not completely prevent it with the hydrophobic membranes. Nanofiltration could be carried out without fouling, at least with the laboratory scale apparatus used here when the flux was below the critical flux. Model substances had a strong form of the critical flux, but the effluents had only a weak form of the critical flux. With the effluents, some fouling always occurred immediately when the filtration was started. However, if the flux was below the critical flux, further fouling was not observed. The flow velocity and pH were probably the most important parameters, along with the membrane properties, that influenced the critical flux. Precleaning of the membranes had only a small effect on the critical flux and retentions, but it improved the permeability of the membranes significantly.