Reduction and Analysis Methods of Indigo

Throughout history indigo was derived from various plants for example Dyer’s Woad (Isatis tinctoria L.) in Europe. In the 19th century were the synthetic dyes developed and nowadays indigo is mainly synthesized from by-products of fossil fuels. Indigo is a so-called vat dye, which means that it needs to be reduced to its water soluble leucoform before dyeing. Nowadays, most of the industrial reduction is performed chemically by sodium dithionite. However, this is considered environmentally unfavourable because of waste waters contaminating degradation products. Therefore there has been interest to find new possibilities to reduce indigo. Possible alternatives for the application of dithionite as the reducing agent are biologically induced reduction and electrochemical reduction. Glucose and other reducing sugars have recently been suggested as possible environmentally friendly alternatives as reducing agents for sulphur dyes and there have also been interest in using glucose to reduce indigo. In spite of the development of several types of processes, very little is known about the mechanism and kinetics associated with the reduction of indigo. This study aims at investigating the reduction and electrochemical analysis methods of indigo and give insight on the reduction mechanism of indigo. Anthraquinone as well as it’s derivative 1,8-dihydroxyanthraquinone were discovered to act as catalysts for the glucose induced reduction of indigo. Anthraquinone introduces a strong catalytic effect which is explained by invoking a molecular “wedge effect” during co-intercalation of Na+ and anthraquinone into the layered indigo crystal. The study includes also research on the extraction of plant-derived indigo from woad and the examination of the effect of this method to the yield and purity of indigo. The purity has been conventionally studied spectrophotometrically and a new hydrodynamic electrode system is introduced in this study. A vibrating probe is used in following electrochemically the leuco-indigo formation with glucose as a reducing agent.

Management of Nitrogen Oxides Reduction Project in a Cement Plant

The main aim of this study was to develop the project management framework model which would serve as the new model to follow for upcoming projects at the Lappeenranta cement plant. The other goal was to execute the SNCR (selective non catalytic reduction) project successfully so that the nitrogen oxides emissions are below the stated emission limit when the new emission limit comes into effect beginning in July, 2008. Nitrogen oxides, project management aspects, SNCR and the invested system are explained in the theory part. In the practical part of the study, the SNCR project in the Lappeenranta cement plant was executed and the findings were documented. In order to reach the aim of this study, a framework of project management was made. The framework is based on the executed SNCR project, previous projects in the cement plant and on the available literature relating to the subject matter. The developed project turned out to be successful.

Role of oxidation-reduction cycle of iron in direct leaching of zinc concentrate

Direct leaching is an alternative to conventional roast-leach-electrowin (RLE) zinc production method. The basic reaction of direct leach method is the oxidation of sphalerite concentrate in acidic liquid by ferric iron. The reaction mechanism and kinetics, mass transfer and current modifications of zinc concentrate direct leaching process are considered. Particular attention is paid to the oxidation-reduction cycle of iron and its role in direct leaching of zinc concentrate, since it can be one of the limiting factors of the leaching process under certain conditions. The oxidation-reduction cycle of iron was experimentally studied with goal of gaining new knowledge for developing the direct leaching of zinc concentrate. In order to obtain this aim, ferrous iron oxidation experiments were carried out. Affect of such parameters as temperature, pressure, sulfuric acid concentration, ferrous iron and copper concentrations was studied. Based on the experimental results, mathematical model of the ferrous iron oxidation rate was developed. According to results obtained during the study, the reaction rate orders for ferrous iron concentration, oxygen concentration and copper concentration are 0.777, 0.652 and 0.0951 respectively. Values predicted by model were in good concordance with the experimental results. The reliability of estimated parameters was evaluated by MCMC analysis which showed good parameters reliability.

Performance of high power fibre laser cutting of thick-section steel and mediumsection aluminium

Cutting of thick section stainless steel and mild steel, and medium section aluminium using the high power ytterbium fibre laser has been experimentally investigated in this study. Theoretical models of the laser power requirement for cutting of a metal workpiece and the melt removal rate were also developed. The calculated laser power requirement was correlated to the laser power used for the cutting of 10 mm stainless steel workpiece and 15 mm mild steel workpiece using the ytterbium fibre laser and the CO2 laser. Nitrogen assist gas was used for cutting of stainless steel and oxygen was used for mild steel cutting. It was found that the incident laser power required for cutting at a given cutting speed was lower for fibre laser cutting than for CO2 laser cutting indicating a higher absorptivity of the fibre laser beam by the workpiece and higher melting efficiency for the fibre laser beam than for the CO2 laser beam. The difficulty in achieving an efficient melt removal during high speed cutting of the 15 mmmild steel workpiece with oxygen assist gas using the ytterbium fibre laser can be attributed to the high melting efficiency of the ytterbium fibre laser. The calculated melt flow velocity and melt film thickness correlated well with the location of the boundary layer separation point on the 10 mm stainless steel cut edges. An increase in the melt film thickness caused by deceleration of the melt particles in the boundary layer by the viscous shear forces results in the flow separation. The melt flow velocity increases with an increase in assist gas pressure and cut kerf width resulting in a reduction in the melt film thickness and the boundary layer separation point moves closer to the bottom cut edge. The cut edge quality was examined by visual inspection of the cut samples and measurement of the cut kerf width, boundary layer separation point, cut edge squareness (perpendicularity) deviation, and cut edge surface roughness as output quality factors. Different regions of cut edge quality in 10 mm stainless steel and 4 mm aluminium workpieces were defined for different combinations of cutting speed and laserpower.Optimization of processing parameters for a high cut edge quality in 10 mmstainless steel was demonstrated

Kulutusteräksen CO2-laserleikkaus

Kandidaatintyö jakaantuu kirjalliseen ja kokeelliseen osaan. Kirjallisessa katsauksessa käsitellään teoriaa erityisesti laserleikkausprosesseja, resonaattorivaihtoehtoja, laserleikkausparametreja, laserleikkauksen etuja ja haittoja sekä kulutusteräksiä. Työn kokeellisessa osassa käsitellään kulutusteräksen Raex 500 laserleikkausta neljälle eri pinnanlaadulle ainevahvuuden ollessa 12 mm.

Novel CO2 Regulated Proteins in Synechocystis PCC 6803

The large biodiversity of cyanobacteria together with the increasing genomics and proteomics metadata provide novel information for finding new commercially valuable metabolites. With the advent of global warming, there is growing interest in the processes that results in efficient CO2 capture through the use of photosynthetic microorganisms such as cyanobacteria. This requires a detailed knowledge of how cyanobacteria respond to the ambient CO2. My study was aimed at understanding the changes in the protein profile of the model organism, Synechocystis PCC 6803 towards the varying CO₂ level. In order to achieve this goal I have employed modern proteomics tools such as iTRAQ and DIGE, recombinant DNA techniques to construct different mutants in cyanobacteria and biophysical methods to study the photosynthetic properties. The proteomics study revealed several novel proteins, apart from the well characterized proteins involved in carbon concentrating mechanisms (CCMs), that were upregulated upon shift of the cells from high CO₂ concentration (3%) to that in air level (0.039%). The unknown proteins, Slr0006 and flavodiiron proteins (FDPs) Sll0217-Flv4 and Sll0219-Flv2, were selected for further characterization. Although slr0006 was substantially upregulated under C_i limiting conditions, inactivation of the gene did not result in any visual phenotype under various environmental conditions indicating that this protein is not essential for cell survival. However, quantitative proteomics showed the induction of novel plasmid and chromosome encoded proteins in deltaslr0006 under air level CO₂ conditions. The expression of the slr0006 gene was found to be strictly dependent on active photosynthetic electron transfer. Slr0006 contains conserved dsRNA binding domain that belongs to the Sua5/YrdC/YciO protein family. Structural modelling of Slr0006 showed an alpha/beta twisted open-sheet structure and a positively charged cavity, indicating a possible binding site for RNA. The 3D model and the co-localization of Slr0006 with ribosomal subunits suggest that it might play a role in translation or ribosome biogenesis. On the other hand, deletions in the sll0217-sll218- sll0219 operon resulted in enhanced photodamage of PSII and distorted energy transfer from phycobilisome (PBS) to PSII, suggesting a dynamic photoprotection role of the operon. Constructed homology models also suggest efficient electron transfer in heterodimeric Flv2/Flv4, apparently involved in PSII photoprotection. Both Slr0006 and FDPs exhibited several common features, including negative regulation by NdhR and ambiguous cellular localization when subjected to different concentrations of divalent ions. This strong association with the membranes remained undisturbed even in the presence of detergent or high salt. My finding brings ample information on three novel proteins and their functions towards carbon limitation. Nevertheless, many pathways and related proteins remain unexplored. The comprehensive understanding of the acclimation processes in cyanobacteria towards varying environmental CO₂ levels will help to uncover adaptive mechanisms in other organisms, including higher plants.

Delay reduction in courts of justice – possibilities and challenges of process improvement in professional public organizations

Delays in the justice system have been undermining the functioning and performance of the court system all over the world for decades. Despite the widespread concern about delays, the solutions have not kept up with the growth of the problem. The delay problem existing in the justice courts processes is a good example of the growing need and pressure in professional public organizations to start improving their business process performance.This study analyses the possibilities and challenges of process improvement in professional public organizations. The study is based on experiences gained in two longitudinal action research improvement projects conducted in two separate Finnish law instances; in the Helsinki Court of Appeal and in the Insurance Court. The thesis has two objectives. First objective is to study what kinds of factors in court system operations cause delays and unmanageable backlogs and how to reduce and prevent delays. Based on the lessons learned from the case projects the objective is to give new insights on the critical factors of process improvement conducted in professional public organizations. Four main areas and factors behind the delay problem is identified: 1) goal setting and performance measurement practices, 2) the process control system, 3) production and capacity planning procedures, and 4) process roles and responsibilities. The appropriate improvement solutions include tools to enhance project planning and scheduling and monitoring the agreed time-frames for different phases of the handling process and pending inventory. The study introduces the identified critical factors in different phases of process improvement work carried out in professional public organizations, the ways the critical factors can be incorporated to the different stages of the projects, and discusses the role of external facilitator in assisting process improvement work and in enhancing ownership towards the solutions and improvement. The study highlights the need to concentrate on the critical factors aiming to get the employees to challenge their existing ways of conducting work, analyze their own processes, and create procedures for diffusing the process improvement culture instead of merely concentrating of finding tools, techniques, and solutions appropriate for applications from the manufacturing sector

Reduction of specific energy consumption of a thermomechanical pulping plant

Kuumahiertoprosessi on erittäin energiaintensiivinen prosessi, jonka energianominaiskulutus (EOK) on yleisesti 2–3.5 MWh/bdt. Noin 93 % energiasta kuluu jauhatuksessa jakautuen niin, että kaksi kolmasosaa kuluu päälinjan ja yksi kolmasosa rejektijauhatuksessa. Siksi myös tämän työn tavoite asetettiin vähentämään energian kulutusta juuri pää- ja rejektijauhatuksessa. Päälinjan jauhatuksessa tutkimuskohteiksi valittiin terityksen, tehojaon ja tuotantotason vaikutus EOK:een. Rejektijauhatuksen tehostamiseen pyrittiin yrittämällä vähentää rejektivirtaamaa painelajittelun keinoin. Koska TMP3 laitoksen jauhatuskapasiteettia on nostettu 25 %, tavoite oli nostaa päälinjan lajittelun kapasiteettia saman verran. Toisena tavoitteena oli pienentää rejektisuhdetta pää- ja rejektilajittelussa ja siten vähentää energiankulutusta rejektijauhatuksessa. Näitä tavoitteita lähestyttiin vaihtamalla päälinjan lajittimiin TamScreen-roottorit ja rejektilajittimiin Metso ProFoil-roottorit ja optimoimalla kuitufraktiot sihtirumpu- ja prosessiparametrimuutoksin. Syöttävällä terätyypillä pystyttiin vähentämään EOK:ta 100 kWh/bdt, mutta korkeampi jauhatusintensiteetti johti myös alempiin lujuusominaisuuksiin, korkeampaan ilmanläpäisyyn ja korkeampaan opasiteettiin. Myös tehojaolla voitiin vaikuttaa EOK:een. Kun ensimmäisen vaiheen jauhinta kuormitettiin enemmän, saavutettiin korkeimmillaan 70 kWh/bdt EOK-vähennys. Tuotantotason mittaamisongelmat heikensivät tuotantotasokoeajojen tuloksia siinä määrin, että näiden tulosten perusteella ei voida päätellä, onko EOK tuotantotasoriippuvainen vai ei. Päälinjan lajittelun kapasiteettia pystyttiin nostamaan TS-roottorilla vain 18 % jääden hieman tavoitetasosta. Rejektilajittelussa pystyttiin vähentämään rejektimäärää huomattavasti Metso ProFoil-roottorilla sekä sihtirumpu- ja prosessiparametrimuutoksin. Lajittamokehityksellä saavutettu EOK-vähennys arvioitiin massarejektisuhteen pienentymisen ja rejektijauhatuksessa käytetyn EOK:n avulla olevan noin 130 kWh/bdt. Yhteenvetona voidaan todeta, että tavoite 300 kWh/bdt EOK-vähennyksestä voidaan saavuttaa työssä käytetyillä tavoilla, mikäli niiden täysi potentiaali hyödynnetään tuotannossa.

Carbonation of Mg(OH)2 in a pressurised fluidised bed for CO2 sequestration

I takt med den ekonomiska tillväxten har CO2-utsläppen till atmosfären ständigt ökat, och utan kraftiga åtgärder kommer de att fortsätta att öka i allt snabbare takt. Konsekvenserna av en påtagligt förhöjd atmosfärisk CO2-halt är fortfarande osäkra (men eventuellt katastrofala) och fenomenet går under namnet global uppvärmning eller klimatförändring. CCS från engelskans ”carbon dioxide capture and storage” framstår som ett alternativ för att bekämpa de ständigt ökande CO2-utsläppen. Ett av de mer intressanta, och för Finlands del ända CCS-alternativet, baserar sig på naturens egna sätt att begränsa atmosfärisk CO2, nämligen vittring. Naturlig vittring, som förenklat innefattar nedbrytningen av sten/berg (även känd som erosion) och de därpå följande reaktionerna med CO2-mättat regnvatten. Slutresultatet är en utfällning av fasta mineraler som nu bundit CO2 i form av kalcium- och magnesiumkarbonat. Kalciumkarbonat är även bättre känt som kalksten, d.v.s. CO2 blir bundet i sten. Det gäller dock att snabba upp denna process, som i naturen är ytterst långsam, på ett ekonomiskt och miljömässigt hållbart sätt. Hittills har ett antal metoder för att påskynda naturlig vittring, eller med andra ord öka CO2-upptagningsförmågan av olika mineraler föreslagits. De mera etablerade uttrycken (lånade från engelskan) talar om mineralkarbonatisering och CO2-mineralisering. Till skillnad från många andra CO2-mineraliseringsalternativ är det alternativ som behandlas i denna avhandling i hög grad baserat på möjligheten att utnyttja den värme som frigörs vid karbonatisering. I teorin är det möjligt att föreställa sig en mineraliseringsprocess som inte kräver extern energi, men tillsvidare har man dock inte lyckats uppnå detta mål. Den process som presenteras i denna avhandling går ut på att man utvinner magnesium ur i naturen vanligt förekommande magnesiumrika mineraler, konverterar det till magnesiumhydroxid och därefter karbonatiserar det till magnesiumkarbonat. I rätta förhållanden kan magnesiumhydroxid reagera med CO2 mycket snabbt och i nuläget har processen potential att minska CO2-utsläppen från industri där spillvärme finns till förfogande (t.ex. cement- och stålindustrin). Fortsatt forskning är dock ett måste för att kunna påverka CO2-utsläppen i en globalt signifikant skala.

Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.

CO2 sparging for improving the filtration properties of iron ore slurries

Iron ore treatment processes are usually continuous and high tonnage and filtration equipment has to meet these requirements. In magnetite (Fe3O4) treatment process continuous rotary disc filters are often used for filtration. Carbon dioxide (CO2) treatment is a fairly novel and un-known filtration enhancing process. The interest to use CO2 is quite high because CO2 is a greenhouse gas that is abundant, readily available and capture and use of CO2 would be environmentally beneficial. The focus of this thesis was to investigate if CO2 could be used to enhance the filtration of magnetite with ceramic disc filter. Previous studies have suggested that CO2 could be used to enhance the filtration properties of different iron ores thus increasing the filtration capacity. In the literature part, the basic theory of filtration and the particle properties affecting filtration were discussed. The basic steps of a typical ore treatment process were presented. The reasons why CO2 might enhance the filtration properties of different ores were investigated. A literature survey of earlier studies of CO2 addition as a filter aid was presented and the basic chemical properties and reactions of CO2 were also discussed. The experimental part was done at the LUT Laboratory of Separation Technology using different magnetite samples from the industry. The filtration experiments indicated that CO2 had a positive influence on the filtration properties of magnetite slurry. Zeta potential of untreated and CO2 treated magnetite was measured and CO2 treated magnetite had lower zeta potential values than the untreated magnetite. The filtration capacity was increased while the cake moisture levels were only slightly increased.

Towards novel biogas upgrading processes

Biogas production has considerable development possibilities not only in Finland but all over the world since it is the easiest way of creating value out of various waste fractions and represents an alternative source of renewable energy. Development of efficient biogas upgrading technology has become an important issue since it improves the quality of biogas and for example facilitating its injection into the natural gas pipelines. Moreover, such upgrading contributes to resolving the issue of increasing CO2 emissions and addresses the increasing climate change concerns. Together with traditional CO2 capturing technologies a new class of recently emerged sorbents such as ionic liquids is claimed as promising media for gas separations. In this thesis, an extensive comparison of the performance of different solvents in terms of CO2 capture has been performed. The focus of the present study was on aqueous amine solutions and their mixtures, traditional ionic liquids, ‘switchable’ ionic liquids and poly(ionic liquid)s in order to reveal the best option for biogas upgrading. The CO2 capturing efficiency for the most promising solvents achieved values around 50 - 60 L CO2 / L absorbent. These values are superior to currently widely applied water wash biogas upgrading system. Regeneration of the solvent mixtures appeared to be challenging since the loss of initial efficiency upon CO2 release was in excess of 20 - 40 vol %, especially in the case of aqueous amine solutions. In contrast, some of the ionic liquids displayed reversible behavior. Thus, for selected “switchable” ionic and poly(ionic liquid)s the CO2 absorption/regeneration cycles were performed 3 - 4 times without any notable efficiency decrease. The viscosity issue, typical for ionic liquids upon CO2 saturation, was addressed and the information obtained was evaluated and related to the ionic interactions. The occurrence of volatile organic compounds (VOCs) before and after biogas upgrading was studied for biogas produced through anaerobic digestion of waste waters sludge. The ionic liquid [C4mim][OAc] demonstrated its feasibility as a promising scrubbing media and exhibited high efficiency in terms of the removal of VOCs. Upon application of this ionic liquid, the amount of identified VOCs was diminished by around 65 wt %, while the samples treated with the aqueous mixture of 15 wt % N-methyldiethanolamine with addition of 5 wt % piperazine resulted in 32 wt % reduction in the amounts of volatile organic compounds only.

Valmistusteknillinen näkökulma hitsattaessa ruostumattomia teräksiä CO2-laserilla

Tämä kandidaatintyö on valmistuksellinen näkökulma ruostumattoman teräksen CO2-laserhitsauksen perusteisiin. Tavoitteena on perehdyttää lukija ruostumattoman teräksen CO2-laserhitsauksen valmistusteknillisiin vaatimuksiin ja teollisuuden sovelluksiin.