Emerging market patterns in recycled paper trade

The international recovered paper trade serves two important functions: increasing raw material availability in the paper and board industry and providing economic incentives to recycle. The purpose of this paper is to shed further light on emerging patterns in this trade by empirically analysing the changes in the bilateral trade flows of recycled paper between 1992 and 2008. According to our estimations, two important changes have taken place in the 1990s and 2000s. First, the growing importance of developing economies in global recycled paper trade plays a significant role in import demand as a determinant of trade flows. Second, the changes in global trade patterns necessitate investigating the transportation cost measures used in applied research.

An Update on Inter-Country Differences in Recovery and Utilization of Recycled Paper

The use of recovered paper as raw material in the paper and board industry has increased heavily during recent decades. At the same time, growing environmental awareness has raised the interest in recycling and a more sustainable way of living, at least in high-income countries. This paper combines these topics and explores how economic, demographic and environmental factors have affected the recovery and utilization of recycled paper between 1992 and 2010 in a sample of 70 countries. This study updates and extends the previous research on the topic using panel data and panel data estimation methods. The results confirm the roles of economic determinants but also indicate that concern for the environment impacts the recovery of recycled paper particularly in high-income countries. Moreover, the motives for recycling appear to depend on the income level of a country, which is something that future policies should consider.

Selvitys erilaisten mäntyöljynkeittoprosessien toiminnasta

Työn tavoitteena oli tutustua eri mäntyöljyprosessien toimintaan. Sulfaattisellun valmistuksessa syntyy sivutuotteena mäntyöljyä. Se tuo lisätuottoa sellutehtaalle. Nykypäivänä mäntyöljyn valmistukseen on kiinnitetty yhä enemmän huomiota uusien jalostusmahdollisuuksien vuoksi. Mäntyöljyä syntyy, kun mustalipeän pinnalta kuorittu suopa palstoitetaan sopivalla hapolla. Suopa koostuu puun uuteaineista eli hartsi- ja rasvahapoista sekä saippuattomista aineista. Suopa pitää erottaa mustalipeästä mahdollisimman hyvin, jotta se ei aiheuttaisi ongelmia sellutehtaan eri prosessin vaiheissa. Suopaa voidaan erottaa mustalipeästä säiliöerotuksena, sentrifugeilla tai hydrosykloneilla. Suovan palstoitusprosessi voi olla erä- tai jatkuvatoiminen prosessi. Jatkuvatoimisia prosesseja ovat: sentrifugi-, säiliödekantointi- ja HDS-prosessi. Mäntyöljyä voidaan käyttää kemianteollisuuden raaka-aineena tai siitä voidaan jalostaa biodieseliä. Tämä biodiesel on niin sanottua toisen polven biopolttoainetta eli se ei sisällä ravinnoksi kelpaavaa raaka-ainetta. Nykypäivänä markkinoilla on sekä eräkeitto- sekä jatkuvatoimisia prosesseja. Suovan erotussäiliöiden rinnalle on tullut uusi sentrifugeilla tapahtuva suovan erotussysteemi.

Palmupohjaisten raaka-aineiden soveltuvuus lämpökynttilämateriaaliksi

Työssä tutkittiin palmupohjaisten raaka-aineiden soveltuvuutta lämpökynttilän valmistukseen steariinin ja parafiinin kanssa. Palmupohjaiset raaka-aineet ovat halvempia kuin steariini ja parafiini, joten raaka-aineen korvaaminen palmupohjaisilla raaka-aineilla voisi tuoda säästöä kynttilänvalmistajalle. Lisäksi niillä voidaan vaikuttaa lämpökynttilän ominaisuuksiin. Teoriaosassa käsiteltiin lämpökynttilän raaka-aineista steariini, parafiini ja palmusteariini. Osassa selitettiin RAL-laatustandardin Quality Mark Candles vaatimukset lämpökynttilälle sekä valuastialle ja keskusteltiin valulämpötilan, jäähdytyksen, viskositeetin ja haaroittuneiden yhdisteiden lukumäärän vaikutuksesta lämpökynttilän koostumukseen. Kokeellisessa osassa valmistettiin lämpökynttilöitä steariinin ja palmupohjaisten raaka-aineiden seoksista palmuraaka-aineiden määrillä 10, 20 ja 30 m- %:a. Parafiinin ja palmusteariinin sekä palmun mid-fraktion seokset valmistettiin palmuraaka-aineiden osuuksilla 10, 20, 40 ja 50 m- %:a ja myös palmusteariinin soft-fraktiolla kokeiltiin seosta 50 m- %:lla. Steariinin ja palmupohjaisten raaka-aineiden seokset eivät toimineet ainakaan käytetyillä sydänlangoilla. Liekinkorkeudet olivat alhaisia eivätkä visuaaliset vaatimukset täyttyneet. Parafiinin ja palmupohjaisten raaka-aineiden seoksista valmistetut kynttilät paloivat ideaalisesti palmuraaka-aineiden osuuksilla 35 – 50 m- %:a. Tulosten perusteella fraktion valinnalla ei näyttänyt olevan merkitystä, mutta palmusteariini on ominaisuuksiensa puolesta kynttilänvalmistukseen soveltuvin. Liekinkorkeus ja palovuo laskivat lineaarisesti palmuraaka-aineen osuuden kasvaessa parafiinikynttilässä.

Modification of Photocatalyst with Enhanced Photocatalytic Activity for Water

Increasing demand and shortage of energy resources and clean water due to the rapid development of industry, population growth and long term droughts have become an issue worldwide. As a result, global warming, long term droughts and pollution-related diseases are becoming more and more serious. The traditional technologies, such as precipitation, neutralization, sedimentation, filtration and waste immobilization, cannot prevent the pollution but restrict the waste chemicals only after the pollution emission. Meanwhile, most of these treatments cannot thoroughly degrade the contaminants and may generate toxic secondary pollutants into ecosystem. Heterogeneous photocatalysis as the innovative wastewater technology attracts many attention, because it is able to generate highly reactive transitory species for total degradation of organic compounds, water pathogens and disinfection by-products. Semiconductor as photocatalysts have demonstrated their efficiency in degrading a wide range of organics into readily biodegradable compounds, and eventually mineralized them to innocuous carbon dioxide and water. But, the efficiency of photocatalysis is limited, and hence, it is crucial issue to modify photocatalyst to enhance photocatalytic activity. In this thesis, first of all, two literature views are conducted. A survey of materials for photocatalysis has been carried out in order to summarize the properties and the applications of photocatalysts that have been developed in this field. Meanwhile, the strategy for the improvement of photocatalytic activity have been explicit discussed. Furthermore, all the raw material and chemicals used in this work have been listed as well as a specific experimental process and characterization method has been described. The synthesize methods of different photocatalysts have been depicted step by step. Among these cases, different modification strategies have been used to enhance the efficiency of photocatalyst on degradation of organic compounds (Methylene Blue or Phenol). For each case, photocatalytic experiments have been done to exhibit their photocatalytic activity.The photocatalytic experiments have been designed and its process have been explained and illustrated in detailed. Moreover, the experimental results have been shown and discussion. All the findings have been demonstrated in detail and discussed case by case. Eventually, the mechanisms on the improvement of photocatalytic activities have been clarified by characterization of samples and analysis of results. As a conclusion, the photocatalytic activities of selected semiconductors have been successfully enhanced via choosing appropriate strategy for the modification of photocatalysts.

Structural dynamics in the global pulp and paper industry

The pulp and paper industry is currently facing broad structural changes due to global shifts in demand and supply. These changes have significant impacts on national economies worldwide. Planted forests (especially eucalyptus) and recovered paper have quickly increased their importance as raw material for paper and paperboard production. Although advances in information and communication technologies could reduce the demand for communication papers, and the growth of paper consumption has indeed flattened in developed economies, particularly in North America and Western Europe, the consumption is increasing on a global scale. Moreover, the focal point of production and consumption is moving from the Western world to the rapidly growing markets of Southeast Asia. This study analyzes how the so-called megatrends (globalization, technological development, and increasing environmental awareness) affect the pulp and paper industry’s external environment, and seeks reliable ways to incorporate the impact of the megatrends on the models concerning the demand, trade, and use of paper and pulp. The study expands current research in several directions and points of view, for example, by applying and incorporating several quantitative methods and different models. As a result, the thesis makes a significant contribution to better understand and measure the impacts of structural changes on the pulp and paper industry. It also provides some managerial and policy implications.

Carbon sources for Power-to-Gas applications in the Finnish energy system

This thesis is done as a part of the NEOCARBON project. The aim of NEOCARBON project is to study a fully renewable energy system utilizing Power-to-Gas or Power-to-Liquid technology for energy storage. Power-to-Gas consists of two main operations: Hydrogen production via electrolysis and methane production via methanation. Methanation requires carbon dioxide and hydrogen as a raw material. This thesis studies the potential carbon dioxide sources within Finland. The different sources are ranked using the cost and energy penalty of the carbon capture, carbon biogenity and compatibility with Power-to-Gas. It can be concluded that in Finland there exists enough CO2 point sources to provide national PtG system with sufficient amounts of carbon. Pulp and paper industry is single largest producer of biogenic CO2 in Finland. It is possible to obtain single unit capable of grid balancing operations and energy transformations via Power-to-Gas and Gas-to-Power by coupling biogas plants with biomethanation and CHP units.

Capillary electrophoresis: Applicability and method validation for biorefinery analytics

Wood-based bioprocesses present one of the fields of interest with the most potential in the circular economy. Expanding the use of wood raw material in sustainable industrial processes is acknowledged on both a global and a regional scale. This thesis concerns the application of a capillary zone electrophoresis (CZE) method with the aim of monitoring wood-based bioprocesses. The range of detectable carbohydrate compounds is expanded to furfural and polydatin in aquatic matrices. The experimental portion has been conducted on a laboratory scale with samples imitating process samples. This thesis presents a novel strategy for the uncertainty evaluation via in-house validation. The focus of the work is on the uncertainty factors of the CZE method. The CZE equipment is sensitive to ambient conditions. Therefore, a proper validation is essential for robust application. This thesis introduces a tool for process monitoring of modern bioprocesses. As a result, it is concluded that the applied CZE method provides additional results to the analysed samples and that the profiling approach is suitable for detecting changes in process samples. The CZE method shows significant potential in process monitoring because of the capability of simultaneously detecting carbohydrate-related compound clusters. The clusters can be used as summary terms, indicating process variation and drift.

Toisen jäte on toisen raaka-aine – Kierrätys ja uudelleenvalmistus taloudellisesti ja ekologisesti kestävänä liiketoimintamahdollisuutena

Toisen jäte on toisen raaka-aine – Kierrätys ja uudelleenvalmistus taloudellisesti ja ekologisesti kestävänä liiketoimintamahdollisuutena Väitöskirjatutkimus tarkastelee kierrätystä ja uudelleenvalmistusta sekä siihen perustuvaa kierrätysliiketoimintaa taloudellisesti ja ekologisesti kestävänä liiketoimintamahdollisuutena. Tässä kestävyys tarkoittaa jätekysymysten ratkaisemista tavalla, joka mahdollistaa kestävän kehityksen periaatteiden mukaisen yhteiskunnan kehittymisen. Jätteisiin liittyvät taloudelliset ja ekolo- giset kysymykset ovat merkittävä yhteiskunnallinen haaste. Tämä luo tarpeen tutkimukselle, jonka lähtökohtana on jätekysymysten moniulotteinen tarkas- telu ja yksittäisen yrityksen toiminnan suhteuttaminen osaksi laajempaa kokonaisuutta. Tässä tutkimuksessa jätteen hyödyntämistä materiaalina lähestytään sekä empiirisesti yrityksen näkökulmasta että teoreettisesti systeemiajattelun tarjoamasta laajemmasta perspektiivistä. Tutkimuksen tavoitteena on ymmär- tää kierrätystä ja uudelleenvalmistusta liiketoimintamahdollisuutena, niiden merkitystä yrityksessä, alueella ja kierrätystaloudessa sekä näiden vuorovai- kutteista suhdetta taloudelliseen ja ekologiseen kestävyyteen nähden. Tutki- muskysymys on tärkeä, koska siihen vastaamalla syvennetään ymmärrystä yrityksissä tapahtuvan kierrätyksen ja uudelleenvalmistuksen merkityksestä kestävämmän yhteiskunnan rakentumisessa. Tutkimuksen teoriaperusta pohjautuu teollisen ekologian kirjallisuuteen ja ekoteollisen kehityksen tutkimukseen. Kierrätysliiketoiminnan kestävyyden tarkastelu rakentuu tutkimuksessa teollisen ekologian ja ekoteollisen kehityk- sen lähtökohtana olevaan win-win-ajatteluun, jonka mukaan hyvä ympäristö- suorituskyky ja hyvä taloudellinen suorituskyky voivat vahvistaa toisiaan. Kierrätysliiketoiminnan teoreettisessa tarkastelussa keskeisiä elementtejä ovat kierrätystalouden malli, teollisen ekologian alueelliset systeemit, ekoteolliset verkostot ja yrityksen rooli teollista ekologiaa soveltavana toimijana. Tutki- muksen keskeisenä kontribuutiona on yritysnäkökulman integroiminen aiem- paa vahvemmin osaksi teollisen ekologian diskursseja. Kierrätysliiketoiminnan taloudelliseen ja ekologiseen kannattavuuteen ja sen myötä kestävyyteen liittyviä kysymyksiä on lähestytty tekemällä yritys- haastatteluja ja hyödyntämällä valmista haastatteluaineistoa. Tutkimusta varten haastattelin 10 kierrätysliiketoimintaa harjoittavaa yritystä vuosina 2007 ja 2008. Tämän lisäksi tutkimuksessa on hyödynnetty Turun ammatti- korkeakoulun ja Turku Science Parkin toteuttamassa RESU-hankkeessa (Kierrätysliiketoiminta ja resurssitehokkuus Varsinais-Suomen vahvuudeksi – RESU) vuosina 2013 ja 2014 kerättyä aineistoa. Hankkeessa haastateltiin yhteensä 25 jätemateriaalia hyödyntävää ja/tai tuottavaa yritystä. Aineistojen analysointimenetelmänä on sisällönanalyysi. Analyysin tulok- sena muodostettiin yhteensä viisi pääteemaa ja 12 alateemaa. Teemat kuvaavat kierrätysliiketoimintaa aiempaa moniulotteisemmin ja näin syventävät ymmär- rystä ilmiön merkityksestä kestävämmän yhteiskunnan rakentumisessa. Teolli- sen ekologian alaan kuuluvat kvalitatiiviset tutkimukset ovat melko harvinai- sia, joten tämän väitöstutkimuksen ilmeisenä vahvuutena on laadullisen tutkimusmenetelmän hyödyntäminen. Tutkimuksen tuloksena voidaan todeta, että kierrätystalouden kehittymistä edistävä kierrätysliiketoiminta on monimuotoista ja sisältää erilaisia liiketoi- mintamahdollisuuksia sekä arvoketjuja. Paikallistuntemus ja keskeinen sijainti jätemateriaalien tuottajien suhteen on tärkeä kriteeri kierrätysliiketoiminnassa, mutta jätemateriaaleja myös kuljetetaan pitkiä matkoja. Paikallisia tai alueelli- sia jätevirtoja hyödyntävä kierrätysliiketoiminta voi tukea alueellista kestä- vyyttä, mutta toisinaan myös keskitetty hyödyntäminen voi olla kestävä vaih- toehto. Yhteistyöverkostot ovat tärkeitä jätemateriaalin laadun ja saatavuuden näkökulmasta. Tutkimus osoittaa, että kierrätysliiketoimintaa harjoittavat yritykset ovat samalla sekä kierrätystalouden käytännön toimeenpanijoita että uuden toimintakulttuurin luojia. Tutkimuksen tulosten perusteella voidaan esittää johtopäätös, että kierrä- tysliiketoiminta on taloudellisesti ja ekologisesti kannattava liiketoimintamah- dollisuus. Win-win-ratkaisut eivät kuitenkaan takaa kierrätysliiketoiminnan kestävyyttä. Kierrätysliiketoiminnan kestävyyden arvioiminen edellyttää laajaa perspektiiviä ja toiminnan vaikutusten suhteuttamista mittakaavaan, ajalliseen ulottuvuuteen, interventioon ja sosiaalisiin kysymyksiin. Teolliseen ekologiaan perustuva kierrätysliiketoiminta luo mahdollisuuksia edistää kestävyyttä, joten tällä perusteella kierrätystä ja uudelleenvalmistusta voidaan pitää kestävänä liiketoimintamahdollisuutena. Avainsanat: kierrätysliiketoiminta, kierrätys, uudelleenvalmistus, systeemiajattelu, teollinen ekologia, ekoteollinen kehitys, kierrätystalous, win-win-ajattelu, kestävyys One company's waste is another's raw material –Recycling and remanufacturing as an economically and environmentally sustainable business opportunity The thesis investigates whether product recycling and remanufacturing can serve as a business opportunity that is economically and ecologically sustaina- ble. In this effort, my idea is to contribute to solving the waste issue in a manner that makes it possible to strive toward sustainable societal develop- ment. The economic and ecological questions associated with waste flows are a significant challenge. The complexity of the issue requires a multidimen- sional approach in which the operation of an individual company is viewed in the context of the larger societal system. In this thesis waste utilization as a resource with value is considered both from an empirical perspective on the firm as well as from a more general viewpoint offered by systems analysis. The objective of the thesis is to under- stand recycling and remanufacturing as a business opportunity. The thesis considers the meaning of recycling and remanufacturing for a single company, for the region the company is located and for the recycling economy. The objective of this study is important for it enhances the understanding of the product recycling and remanufacturing processes that take place within busi- ness organizations and how these processes affect societal sustainable development. The theoretical basis arises from industrial ecology and from the literature on eco-industrial development. The business-economic win-win situation and this vision serve as the basic position from which recycling business is inves- tigated in the thesis. In the theoretical discussion, key elements are recycling economy model, regional and local industrial ecosystems, eco-industrial networks and the role of a company as an actor that applies industrial ecology in practice. The main contribution of this study lies in integrating the company perspective more strongly into the industrial ecology discourses. The recycling business has been studied by conducting interviews in companies and by secondary analysis of an existing interview material. During 2007 and 2008 I made 10 interviews in companies that are active in recycling business. In addition, I used interview material gathered for the project “Recycling business and resource efficiency as the strength of Southwest Finland” (RESU) by Turku University of Applied Sciences and Turku Science Park during the period 2013–2014. This data covers altogether 25 businesses that either utilize and/or produce waste materials. The data has been analyzed using the content analysis method. This process led to the development of 5 main themes and 12 sub-themes. These themes describe the recycling business multi-dimensionally and thus understanding of the phenomenon and its role in building a sustainable society are substantially deepened in this research. In the field of industrial ecology qualitative studies are relatively rare and therefore the qualitative research approach is an evident strength of the thesis. The results show that the recycling business activity supporting recycling economy has diverse dimensions including various business opportunities and diverse value chains. The results show that for waste producers it is important to know the local situational factors and to have a central geographical location. Waste materials are, however, transported over long distances as well. The study indicates that local waste flow utilization can support regional sustainability, while occasionally a more centralized utilization can be sustain- able. Collaboration networks are important to secure the quality and availabil- ity of utilizable waste materials. The thesis demonstrates that the companies practicing recycling business serve simultaneously as actors that implement recycling economy and enhance a new operation culture within the business community. The overall conclusion of the thesis argues that recycling business is a business opportunity that can support both an economically and environmen- tally viable business operation. However, win-win solutions do not secure the sustainability of recycling business. The sustainability evaluation of recycling business requires a holistic systems perspective. The actions undertaken need to be considered with changing spatial and temporal system boundaries, societal intervention and placed in the context of relevant societal issues. Industrial ecology -based recycling business creates opportunities for sustain- ability and thus recycling and remanufacturing present an opportunity for sustainable business. Keywords: Recycling business; Recycling; Remanufacturing, Systems thinking; Industrial ecology; Eco-industrial development; Recycling Economy; Win-Win thinking; Sustainability

Enhancement of ultrafiltration process by pretreatment in recovery of hemicelluloses from wood extracts

Hemicelluloses are potential raw material for several items produced in future wood-based biorefineries. One possible method for recovering hemicelluloses from wood extracts is ultrafiltration (UF). However, low filtration capacities and severe fouling restrict the use of tight UF membranes in the treatment of wood extracts. The lack of suitable commercial membranes creates a need for pretreatment which would decrease fouling and increase the filtration capacity. This thesis focuses on the evaluation of the possibility to improve the filtration capacity and decrease fouling with the pretreatment of wood extracts. Methods which remove harmful compounds and methods which degrade them are studied, as well as combinations of the methods. The tested pretreatments have an influence on both the concentration of different compounds and the molecular mass distribution of the compounds in the extract. This study revealed that in addition to which kind of compounds were removed, also the change in molecular size distribution affected the filtration capacity significantly. It was shown that the most harmful compounds for the filtration capacity of the hydrophobic 5 kDa membrane were the ones capable of permeating the membrane and fouling also the inner membrane structure. Naturally, the size of the most harmful compounds depends on the used UF membrane and is thus case-specific. However, in the choice of the pretreatment method, the focus should be on the removal of harmful compound sizes rather than merely on the total amount of removed foulants. The results proved that filtration capacity can be increased with both adsorptive and oxidative pretreatments even by hundreds of per cents. For instance, the use of XAD7 and XAD16 adsorbents increased the average flux in the UF of a birch extract from nearly zero to 107 kg/(m2h) and 175 kg/(m2h), respectively. In the treatment of a spruce extract, oxidation by pulsed corona discharge (PCD) increased the flux in UF from 46 kg/(m2h) to 158 kg/(m2h). Moreover, when a birch extract batch was treated with laccase enzyme, the flux in UF increased from 15 kg/(m2h) to 36 kg/(m2h). However, fouling was decreased only by adsorptive pretreatment while oxidative methods had a negligible or even negative impact on it. This demonstrates that filtration capacity and fouling are affected by different compounds and mechanisms. The results of this thesis show that filtration capacity can be improved and fouling decreased through appropriate pretreatment. However, the choice of the best possible pretreatment is case-specific and depends on the wood extract and the membrane used. Finding the best option requires information on the extract content and membrane characteristics as well as on the filtration performance of the membrane in the prevailing conditions and a multivariate approach. On the basis of this study, it can be roughly concluded that adsorptive pretreatment improves the filtration capacity and decreases fouling rather reliably, but it may lead to significant hemicellulose losses. Oxidation reduces the loss of valuable hemicelluloses and could improve the filtration capacity, but fouling challenges may remain. Combining oxidation with adsorptive pretreatment was not a solution for avoiding hemicellulose losses in the tested cases.

Kartoitus Kaakkois-Suomen jätelietteistä, lietteen tuottajista ja käsittelymenetelmistä

In this thesis the sludge of Southeastern-Finland, the companies which produce sludge and the current methods and those still in development have been surveyed. 85 % of the waste sludge from industry comes from forest industries. The sludge from municipal waste water treatment plants is mostly used as a raw material for bioplants. The sludge from forest industry is mostly incinerated. New circulation methods increase the recycling value of the waste by creating new products but they still lack a full-scale plant. The political pressure from Europe and the politics driven by the government of Finland will drive circular economy forward and thus uplifting the processing options of waste slurries. This work is divided in two parts, first contains the survey and the second contains the experimental part and the operational methods based on the survey. In the experimental part wet hard sheet waste sludge was de-watered with shaking filter and the applications for waste sludge from cellulose factory were considered. The results are, that the wet hard sheet waste sludge can be dewatered to high enough total solids content for the inteded use. Also, the cellulose waste sludge has too high Cd content in almost all of the batches to be used as a land improment.

The Competitive Analysis of Selected Biorefineries in Finland

Biorefineries is a perspective field of study that covers many opportunities of a successful business unit with respect to sustainability. The thesis focuses on the following key objective: identification of a competitive biorefineries production process in small and medium segments of the chemical and forest industries in Finland. The scope of the research relates to the selected biorefineries operations in Finland and the use of hemicellulose, as a raw material. The identification of the types of biorefineries and the important technical and process characteristics opens the advantage in the company’s competitive analysis. The study concentrates on the practical approach to the scientific methods of the market and companies research with the help of Quality Function Deployment and House of Quality tool. The thesis’s findings provide mindset version of the expert’s House of Quality application, identification of crucial biorefineries technical and design characteristics’ correlation and their effect on the competitive behavior of a company. The theoretical background helps to build the picture of the problematic issues within the field and provides scientific possible solutions. The analysis of the biorefineries’ market and companies operations bring the practical-oriented aptitude of the research. The results of the research can be used for the following investigations in a field and may be applied as a company’s management analytic and strategic application.

Derivative hedging strategies for bitumen price risk

The objective of the study is to extend the existing hedging literature of the commodity price risks by investigating what kind of hedging strategies can be used in companies using bitumen as raw material in their production. Five different alternative swap hedging strategies in bitumen markets are empirically tested. Strategies tested are full hedge strategy, simple, conservative, and aggressive term structure strategies, and implied volatility strategy. The effectiveness of the alternative strategies is measured by excess returns compared to no hedge strategy. In addition, the downside risk of each strategy is measured with target absolute semi-deviation. Results indicate that any of the tested strategies does not outperform the no hedge strategy in terms of excess returns in all maturities. The best-performing aggressive term structure strategy succeeds to create positive excess returns only in short maturities. However, risk seems to increase hand-in-hand with the excess returns so that the best-performing strategies get the highest risk metrics as well. This implicates that the company willing to gain from favorable price movements must be ready to bear a greater risk. Thus, no superior hedging strategy over the others is found.

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.