Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

Kaatopaikkakaasujen käsittelyn kehittäminen Korvenmäen kaatopaikalla

Työssä tutkittiin Salossa sijaitsevan Korvenmäen kaatopaikan kaasunkeräysjärjestelmää. Tavoitteena oli selvittää kaatopaikkakaasun talteenoton merkittävimmät haasteet, löytää ratkaisuja ongelmiin ja hajuhaittojen vähentämiseen sekä arvioida keräysjärjestelmän parannusten ja kaatopaikalle tulevan pintarakenteen vaikutus talteenottoon ja hajuhaittoihin. Korvenmäen kaatopaikalla on käytössä vaakakeräysjärjestelmä, jonka merkittävimpiä ongelmia ovat olleet kaatopaikkakaasun matala talteenottoaste, happipitoisuuden nousu, järjestelmän hankala säädettävyys sekä kaatopaikalla ja ympäristössä havaitut hajuhaitat. Muodostuvan ja karkaavan kaatopaikkakaasun määrää arvioitiin Jouko Petäjän metaanilaskentamallin avulla. Tulosten perusteella kaasua muodostuu runsaasti, mutta suurin osa siitä pääsee karkaamaan ympäristöön, sillä arvioitu kaatopaikkakaasun talteenottoaste on tällä hetkellä vain 11 %. Kaasujen käsittelykäytäntöjä suomalaisilla kaatopaikoilla selvitettiin kyselytutkimuksella. Tutkimuksen mukaan kaasunkeräyksen ongelmat ja hajuhaitat ovat yleisiä, mutta erilaisilla toimenpiteillä niitä voidaan huomattavasti vähentää. Korvenmäelle suositeltavia kehitystoimia ovat kaasulinjoihin yhdistettyjen suotoveden keräys- ja tarkkailukaivojen tiivistäminen, vanhojen vaakalinjojen kunnon tarkistus ja korjaus sekä pystykaivojen asentaminen kaasunkeräyksen tehostamiseksi. Pintarakenne tulee valmistuttuaan vähentämään karkaavan kaasun ja kaasulinjoihin imeytyvän ilman määrää. Hajuhaittojen hallinnassa tärkeintä on toimiva kaasunkeräys, mutta lisäksi suositellaan rikkivetyä hapettavien päivittäispeittomateriaalien levittämistä kaatopaikan pinnalle. Kehitystoimenpiteiden myötä kaatopaikkakaasun talteenottoaste tulee paranemaan ja hajuhaitat vähenevät. Kerättävän kaasumäärän kasvaessa mikroturbiinilaitoksen kapasiteettia voidaan lisätä, jotta kaasu saadaan mahdollisimman tehokkaasti hyödynnettyä energiana.

CFD modeling of dispersion water feed in wastewater cleaning application

Fluid particle breakup and coalescence are important phenomena in a number of industrial flow systems. This study deals with a gas-liquid bubbly flow in one wastewater cleaning application. Three-dimensional geometric model of a dispersion water system was created in ANSYS CFD meshing software. Then, numerical study of the system was carried out by means of unsteady simulations performed in ANSYS FLUENT CFD software. Single-phase water flow case was setup to calculate the entire flow field using the RNG k-epsilon turbulence model based on the Reynolds-averaged Navier-Stokes (RANS) equations. Bubbly flow case was based on a computational fluid dynamics - population balance model (CFD-PBM) coupled approach. Bubble breakup and coalescence were considered to determine the evolution of the bubble size distribution. Obtained results are considered as steps toward optimization of the cleaning process and will be analyzed in order to make the process more efficient.

Simulation of the Interaction Mean Free Path between Neutrons and TRISO Particles

The interaction mean free path between neutrons and TRISO particles is simulated using scripts written in MATLAB to solve the increasing error present with an increase in the packing factor in the reactor physics code Serpent. Their movement is tracked both in an unbounded and in a bounded space. Their track is calculated, depending on the program, linearly directly using the position vectors of the neutrons and the surface equations of all the fuel particles; by dividing the space in multiple subspaces, each of which contain a fraction of the total number of particles, and choosing the particles from those subspaces through which the neutron passes through; or by choosing the particles that lie within an infinite cylinder formed on the movement axis of the neutron. The estimate from the current analytical model, based on an exponential distribution, for the mean free path, utilized by Serpent, is used as a reference result. The results from the implicit model in Serpent imply a too long mean free path with high packing factors. The received results support this observation by producing, with a packing factor of 17 %, approximately 2.46 % shorter mean free path compared to the reference model. This is supported by the packing factor experienced by the neutron, the simulation of which resulted in a 17.29 % packing factor. It was also observed that the neutrons leaving from the surfaces of the fuel particles, in contrast to those starting inside the moderator, do not follow the exponential distribution. The current model, as it is, is thus not valid in the determination of the free path lengths of the neutrons.

Decision making and decision support in service systems

This thesis is a literature study that develops a conceptual model of decision making and decision support in service systems. The study is related to the Ä-Logi, Intelligent Service Logic for Welfare Sector Services research project, and the objective of the study is to develop the necessary theoretical framework to enable further research based on the research project results and material. The study first examines the concepts of service and service systems, focusing on understanding the characteristics of service systems and their implications for decision making and decision support to provide the basis for the development of the conceptual model. Based on the identified service system characteristics, an integrated model of service systems is proposed that views service systems through a number of interrelated perspectives that each offer different, but complementary, implications on the nature of decision making and the requirements for decision support in service systems. Based on the model, it is proposed that different types of decision making contexts can be identified in service systems that may be dominated by different types of decision making processes and where different types of decision support may be required, depending on the characteristics of the decision making context and its decision making processes. The proposed conceptual model of decision making and decision support in service systems examines the characteristics of decision making contexts and processes in service systems, and their typical requirements for decision support. First, a characterization of different types of decision making contexts in service systems is proposed based on the Cynefin framework and the identified service system characteristics. Second, the nature of decision making processes in service systems is proposed to be dual, with both rational and naturalistic decision making processes existing in service systems, and having an important and complementary role in decision making in service systems. Finally, a characterization of typical requirements for decision support in service systems is proposed that examines the decision support requirements associated with different types of decision making processes in characteristically different types of decision making contexts. It is proposed that decision support for the decision making processes that are based on rational decision making can be based on organizational decision support models, while decision support for the decision making processes that are based on naturalistic decision making should be based on supporting the decision makers’ situation awareness and facilitating the development of their tacit knowledge of the system and its tasks. Based on the proposed conceptual model a further research process is proposed. The study additionally provides a number of new perspectives on the characteristics of service systems, and the nature of decision making and requirements for decision support in service systems that can potentially provide a basis for further discussion and research, and support the practice alike.

Mathematical modeling and optimal control of malaria

Malaria continues to infect millions and kill hundreds of thousands of people worldwide each year, despite over a century of research and attempts to control and eliminate this infectious disease. Challenges such as the development and spread of drug resistant malaria parasites, insecticide resistance to mosquitoes, climate change, the presence of individuals with subpatent malaria infections which normally are asymptomatic and behavioral plasticity in the mosquito hinder the prospects of malaria control and elimination. In this thesis, mathematical models of malaria transmission and control that address the role of drug resistance, immunity, iron supplementation and anemia, immigration and visitation, and the presence of asymptomatic carriers in malaria transmission are developed. A within-host mathematical model of severe Plasmodium falciparum malaria is also developed. First, a deterministic mathematical model for transmission of antimalarial drug resistance parasites with superinfection is developed and analyzed. The possibility of increase in the risk of superinfection due to iron supplementation and fortification in malaria endemic areas is discussed. The model results calls upon stakeholders to weigh the pros and cons of iron supplementation to individuals living in malaria endemic regions. Second, a deterministic model of transmission of drug resistant malaria parasites, including the inflow of infective immigrants, is presented and analyzed. The optimal control theory is applied to this model to study the impact of various malaria and vector control strategies, such as screening of immigrants, treatment of drug-sensitive infections, treatment of drug-resistant infections, and the use of insecticide-treated bed nets and indoor spraying of mosquitoes. The results of the model emphasize the importance of using a combination of all four controls tools for effective malaria intervention. Next, a two-age-class mathematical model for malaria transmission with asymptomatic carriers is developed and analyzed. In development of this model, four possible control measures are analyzed: the use of long-lasting treated mosquito nets, indoor residual spraying, screening and treatment of symptomatic, and screening and treatment of asymptomatic individuals. The numerical results show that a disease-free equilibrium can be attained if all four control measures are used. A common pitfall for most epidemiological models is the absence of real data; model-based conclusions have to be drawn based on uncertain parameter values. In this thesis, an approach to study the robustness of optimal control solutions under such parameter uncertainty is presented. Numerical analysis of the optimal control problem in the presence of parameter uncertainty demonstrate the robustness of the optimal control approach that: when a comprehensive control strategy is used the main conclusions of the optimal control remain unchanged, even if inevitable variability remains in the control profiles. The results provide a promising framework for the design of cost-effective strategies for disease control with multiple interventions, even under considerable uncertainty of model parameters. Finally, a separate work modeling the within-host Plasmodium falciparum infection in humans is presented. The developed model allows re-infection of already-infected red blood cells. The model hypothesizes that in severe malaria due to parasite quest for survival and rapid multiplication, the Plasmodium falciparum can be absorbed in the already-infected red blood cells which accelerates the rupture rate and consequently cause anemia. Analysis of the model and parameter identifiability using Markov chain Monte Carlo methods is presented.

Chemical changes in biomass during torrefaction

Torrefaction is moderate thermal treatment (~200-300 °C) of biomass in an inert atmosphere. The torrefied fuel offers advantages to traditional biomass, such as higher heating value, reduced hydrophilic nature, increased its resistance to biological decay, and improved grindability. These factors could, for instance, lead to better handling and storage of biomass and increased use of biomass in pulverized combustors. In this work, we look at several aspects of changes in the biomass during torrefaction. We investigate the fate of carboxylic groups during torrefaction and its dependency to equilibrium moisture content. The changes in the wood components including carbohydrates, lignin, extractable materials and ashforming matters are also studied. And at last, the effect of K on torrefaction is investigated and then modeled. In biomass, carboxylic sites are partially responsible for its hydrophilic characteristic. These sites are degraded to varying extents during torrefaction. In this work, methylene blue sorption and potentiometric titration were applied to measure the concentration of carboxylic groups in torrefied spruce wood. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic group contents. Thus, both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction. This provides new information to the chemical changes occurring during torrefaction. The effect of torrefaction temperature on the chemistry of birch wood was investigated. The samples were from a pilot plant at Energy research Center of the Netherlands (ECN). And in that way they were representative of industrially produced samples. Sugar analysis was applied to analyze the hemicellulose and cellulose content during torrefaction. The results show a significant degradation of hemicellulose already at 240 °C, while cellulose degradation becomes significant above 270 °C torrefaction. Several methods including Klason lignin method, solid state NMR and Py-GC-MS analyses were applied to measure the changes in lignin during torrefaction. The changes in the ratio of phenyl, guaiacyl and syringyl units show that lignin degrades already at 240 °C to a small extent. To investigate the changes in the extractives from acetone extraction during torrefaction, gravimetric method, HP-SEC and GC-FID followed by GC-MS analysis were performed. The content of acetone-extractable material increases already at 240 °C torrefaction through the degradation of carbohydrate and lignin. The molecular weight of the acetone-extractable material decreases with increasing the torrefaction temperature. The formation of some valuable materials like syringaresinol or vanillin is also observed which is important from biorefinery perspective. To investigate the change in the chemical association of ash-forming elements in birch wood during torrefaction, chemical fractionation was performed on the original and torrefied birch samples. These results give a first understanding of the changes in the association of ashforming elements during torrefaction. The most significant changes can be seen in the distribution of calcium, magnesium and manganese, with some change in water solubility seen in potassium. These changes may in part be due to the destruction of carboxylic groups. In addition to some changes in water and acid solubility of phosphorous, a clear decrease in the concentration of both chlorine and sulfur was observed. This would be a significant additional benefit for the combustion of torrefied biomass. Another objective of this work is studying the impact of organically bound K, Na, Ca and Mn on mass loss of biomass during torrefaction. These elements were of interest because they have been shown to be catalytically active in solid fuels during pyrolysis and/or gasification. The biomasses were first acid washed to remove the ash-forming matters and then organic sites were doped with K, Na, Ca or Mn. The results show that K and Na bound to organic sites can significantly increase the mass loss during torrefaction. It is also seen that Mn bound to organic sites increases the mass loss and Ca addition does not influence the mass loss rate on torrefaction. This increase in mass loss during torrefaction with alkali addition is unlike what has been found in the case of pyrolysis where alkali addition resulted in a reduced mass loss. These results are important for the future operation of torrefaction plants, which will likely be designed to handle various biomasses with significantly different contents of K. The results imply that shorter retention times are possible for high K-containing biomasses. The mass loss of spruce wood with different content of K was modeled using a two-step reaction model based on four kinetic rate constants. The results show that it is possible to model the mass loss of spruce wood doped with different levels of K using the same activation energies but different pre-exponential factors for the rate constants. Three of the pre-exponential factors increased linearly with increasing K content, while one of the preexponential factors decreased with increasing K content. Therefore, a new torrefaction model was formulated using the hemicellulose and cellulose content and K content. The new torrefaction model was validated against the mass loss during the torrefaction of aspen, miscanthus, straw and bark. There is good agreement between the model and the experimental data for the other biomasses, except bark. For bark, the mass loss of acetone extractable material is also needed to be taken into account. The new model can describe the kinetics of mass loss during torrefaction of different types of biomass. This is important for considering fuel flexibility in torrefaction plants.

Innovatiivisten ja funktionaalisten tuotteiden kysynnän ennustaminen terveydenhuollonalan tukkuyrityksessä

Tässä diplomityössä tutkitaan miten kysyntää voidaan ennustaa erityyppisille tuotteille. Työssä esitellään miten funktionaaliset ja innovatiiviset tuotteet poikkeavat toisistaan sekä miten niiden toimitusketjut eroavat. Työssä esitellään kvantitatiivisia ja kvalitatiivisia menetelmiä kysynnän ennustamiseen erityyppisille tuotteille ja sitä kuinka ennustemenetelmä tulisi tuotteille valita. Työssä käydään läpi ennusteprosessi, ennusteiden suorituskyvyn mittaaminen ja ennustamisen hyödyt ja sudenkuopat. Työn käytännönosuus on tehty kohdeyritykselle, joka toimii terveydenhuollonalan maahantuojana ja tukkuyrityksenä. Työn tarkoituksena on luoda yritykselle ennusteenvalintatyökalu, jonka avulla voidaan valita yrityksen toisistaan poikkeaville tuotteille tarpeeseen sopivia kysynnän ennusteita. Työssä luodaan ennusteet neljälle yrityksen toisistaan poikkeavalle tuoteryhmälle, joista jokaisella on erilainen tarve ennusteen käytölle. Jokaisesta tuoteryhmästä on valittu yhdestä kolmeen tuotetta, joille luodaan ennusteet käyttäen yhtä tai kahta erilaista menetelmää ja niiden suoriutumista verrataan yksinkertaisimpaan menetelmään, naiiviin menetelmän tuloksiin.

Natural freeze crystallization : purification of aqueous Na2SO4 solutions with cold air

The aim of this thesis was to examine efficiency of freeze crystallization and eutectic freeze crystallization in purification of wastewater by imitating natural freezing. In addition, a mathematic model based on heat transfer to determine ice thickness and ice growth rate was examined. Also, the amount of sodium sulfate crystallized at the eutectic point was under investigation. In literature part, advantages and applications of the freeze crystallization are discussed, and possibility to apply it in Northern hemisphere winter weather conditions is under study. Furthermore, main sources of sodium sulfate from Finnish industries are described. The experiments were carried out in modified chest freezer, where a fan was placed in order to obtain laminar air flow inside. Picolog PT-104 data logger was used to monitor temperature changes in the salt-water solution, and constant temperature was maintained in the crystallizer with Lauda RP 850 thermostat. The impurity of formed ice layer was determined by weighing ice samples after experiment and again after 24 hours drying to full dryness in oven. Volume of salt-water solution was also measured after experiment. The highest purity of formed ice layer was obtained with small temperature difference and with long freezing time. On the other hand, the amount of crystallized sodium sulfate was its greatest with long freezing time and higher temperature difference. The results obtained by the mathematic model and empirical results did not differ significantly in most of the experiments. However, the difference increased when salt-water mixture reached its eutectic point, leading to simultaneous ice and salt crystallization. Eutectic point was reached only with the highest salt concentration with one exception. In these cases, calculated values were in many cases greater than the experimental ones. In winter weather conditions freeze crystallization is cost-effective wastewater treatment method and rather simple. Nonetheless, the efficiency and separation rate are strongly depended on ambient temperature and its changes

Toimintokohtainen kustannuslaskenta muovialan teollisuusyrityksessä

Jatkuva teknologioiden kehittyminen ja globaalin talousjärjestelmän lainalaisuudet pakottavat yrityksiä kiinnittämään enenevässä määrin huomiota kilpailukykyyn ja kannattavuuteen. Kustannuslaskennan tarkkuus on yksi tärkeimmistä taloushallinnon elementeistä kilpailukyvyn ylläpitämisessä. Virheisiin ei ole varaa, sillä väärin perustein tehdyt kustannuslaskennat ajavat yrityksen nopeasti taloudellisiin vaikeuksiin. Tässä tutkimuksessa oli tavoitteena etsiä teollisen muovialan yrityksen tarpeisiin parhaiten sopiva kustannuslaskentajärjestelmä. Tutkimuksen teoriaosassa tutustuttiin eri kustannuslaskentamenetelmiin, ja tarkemmin toimintolaskennan yksinkertaisempaan muotoon, aikaperusteiseen toimintolaskentaan, sen toimivuuden ja käytettävyyden kannalta. Tutkimus toteutettiin konstruktiivisena case -tutkimuksena, jossa pyrittiin kuvaamaan ja havainnollistamaan uusi laskentamalli eli konstruktio. Tutkimuksen empiirisessä osuudessa suoritettiin esimerkkilaskelmia case yrityksen valmistamalle tuoteryhmälle ja vertailtiin laskelman tuloksia nykyiseen laskentamalliin. Saatujen tietojen pohjalta yritys pystyy muokkaamaan hinnoittelua vastaamaan kannattavuustavoitteita ja parantamaan kilpailukykyään, sillä malli tuottaa tarkempaa tietoa kustannuksista ja asiakaskohtaisista kannattavuuksista.

A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.

Palveluruokamarkkinoiden innovatiivisen toimintamallin suunnittelu

Diplomityön tavoitteena on ollut kehittää elintarvikeyrityksen palveluruokamarkkinoille uusi innovatiivinen toimintamalli haastattelujen, havainnoinnin ja kirjallisuuden perusteella. Tutkimusongelman päätutkimuskysymys on: Miten yrityksen palveluruoka- eli valmisruokatuotteille suunnitellaan innovatiivinen toimintamalli tuoteperheen ja jakelun suhteen? Tavoitteena on kartoittaa yrityksen palveluruoan nykytilanne ja luoda toimintamalli, joka toisi yritykselle selkeää lisäarvoa ja kilpailuetua. Teoreettisessa osuudessa selvitetään elintarviketeollisuuden, valmisruoan ja elintarvikelogistiikan tilannetta suomalaisesta ja globaalista näkökulmasta. Työssä on tarkasteltu elintarvikepuolen nykytilannetta ja tulevaisuuden suuntauksia tuotteiden, ruokailutottumusten ja logistiikan osalta. Innovaatioiden osalta työ painottuu palveluruokapuolen konseptin ja uuden logistisen yhteistyöhön pohjautuvan mallin kehittämiseen. Työn käytännön osiossa on tehty case-tutkimus ”yrityksen palveluruoan nykytilanne tuotteiden ja logistiikan osalta”. Toimialan markkinatilannetta on kartoitettu, jotta hahmotetaan, missä on potentiaalisimmat markkinat palveluruoalle. Työn tavoitteena on ollut kehittää Hoviruoka Oy:lle palveluruoan segmentointiin ja logistiikkaan liittyvä innovatiivinen toimintamalli. Toimintamallin avulla yritys saa kilpailuetua ja taloudellista hyötyä kilpailijoihin nähden, ja on edelläkävijä kyseisen toimintamallin ansiosta. Työn tuloksissa on käsitelty keskeiset tulokset ja mahdolliset jatkotoimenpiteet. Työssä kehitettiin yritykselle uusi toimintamalli palveluruoka puolelle. Työlle asetetut tavoitteet saavutettiin kaikkien kolmen - tekijän, yliopiston ja yrityksen - kannalta.